The race will see the men's peloton tackle 257km through the hills of Wallonia, while the women's peloton take on a 142km from Bastogne north.
Despite reigning champion Tadej Pogačar (UAE Team Emirates) missing out through illness, there are still plenty of major names at both races, from the 2021 women's winner Demi Vollering (SD Worx) to world champion Julian Alaphilippe (QuickStep-AlphaVinyl).
Here's what they had to say ahead of the races on Sunday morning.
Julian Alaphilippe (QuickStep-AlphaVinyl)
"I've already forgotten my fourth place on Wednesday, I'm just happy and motivated to be at the start here. I'm focused and happy too. The weather is good, the team is solid and we'll give our maximum.
"Well, above all it's bad news for [Pogačar]. I'm not really thinking about that, I'm focused on my race.
"UAE have still brought a very strong team so we'll see if they want to control things or if they want to make the race hard like some other teams. We'll have to see and we'll have to be prepared for lots of scenarios.
"It's Remco's first participation but we know that he has the ability to win already. We'll see how it plays out in the finale. If he wins, I would be very happy."
Demi Vollering (SD Worx)
"I really like this race. It's always nice to race here. It's a hard race and that's also what I like. I always ride here with so much motivation and it's also a bit where it all started for me.
"I think we need to feel how the race goes but I think it will be a hard, aggressive race. It's also a race where you can't hide so much, so that's also important here."
Michael Matthews (BikeExchange-Jayco)
"Hopefully good. Last night wasn't so good. Unfortunately I missed out on Flèche also and I was vomiting most of the night so hopefully I can come round this morning. I have to be honest, it's not been a great week for me this week.
"I came here really prepared for Flèche and Liège but with what happened overnight it's going to be a very difficult race but I'll try my best and see what I have.
"Hopefully I'm there [in the final]. I think it's a headwind on the way back so hopefully it makes the race a little bit slower and I can get as far as possible. The shape is really good so hopefully I can pull something out of the bag today.
"I was really excited for today and still am obviously but what happened over night is going to make it really difficult. I still have high hopes and we are still very confident and we will still try our best."
Matej Mohoric (Bahrain Victorious)
"I hope good. I'll see how my climbing legs are today. We're definitely motivated as a team, everybody is healthy and fit, and we'll do our best to try and win this race.
"We need to be honest with each other. Of course, not all of us can win. We'll have to decide in the final who we ride for. Dylan is probably the rider in the best shape at the moment after winning Fleche on Wednesday. He'll go well today, for sure. We have some others who are going well so we'll make sure to have a good go.
"We will see. I think you need to see how the other teams who want to control the final are, and how strong the leaders are. Then we will decide."
Annemiek van Vleuten (Movistar)
"It's not stressful. I like this race. It's a super nice opportunity to play it again.
"I took some confidence from my second place in Flèche. It was my second time on the podium without having a breakaway. This race suits me better because the climbs are a bit long. So, for the Ardennes, this one is my favourite.
"For sure I won't wait until the last few hundred metres. For me, I'll use the climbs and also race it with my team because we also have Arlenis Sierra, a super-fast rider who can climb well. She's a good card to play."
Marc Hirschi (UAE Team Emirates)
"Yes it changed the team but in the end there are more important things than cycling. It's only a race. We have a strong team here. Our tactics are more open now because we have a lot of good riders, maybe no top favourite, but a lot of good riders. So, we'll try to race offensive today.
"I have a protected role but we want to everybody have his chancec to go. We want to race together but a lot of riders in our team have the chance today to go for a result."
Michal Kwiatkowski (Ineos Grenadiers)
"Big block [of racing] but an exciting block. It will be nice to finish off with Liège-Bastogne-Liège before a break.
"It is a nasty one, you have to be on a good day, obviously a lot of ascending metres. The distance and the history of the race just show that the strongest guy wins and hopefully as a collective team we can play our cards in the final and go for the win- that's our objective.
"It's still a kind of unpredictable race in terms of what's going to happen from the top of La Redoute which is obviously a very tough climb. From the top of La Roche-aux-Faucons it's 11 kilometres and there was always some movements from riders, we've seen in the past.
"It's been raced from a small group for the victory but you can go solo, we just have to pay attention and just play with the cards and with the other rivals, what the race will bring. It's hard to say, you just have to be open-minded and feel the race."
Floortje Mackaij (Team DSM)
"I'm always happy to come back here. Last year we missed it but today we're ready for another one and I'm really looking forward to it.
"I think this race can go a lot of different ways. It's a hard parcours, especially from halfway onwards, so I think we have a strong team here and we can come far – also with an early attack.
"I think we have more cards to play [than Liane]. That's nice, we all have our own strengths so it can go different ways."
Remco Evenepoel (QuickStep-AlphaVinyl)
"We have to make it a fun, good race. Hopefully not too 'closed', because then everyone knows who is the fastest.
"The wind is disadvantageous from Bastogne until the hill zone, so it will be 'a walk' until there, so to speak. After that we will see. I think there are still teams that benefit from an open race, I think of Movistar and Bahrain.
"It's not my job to break open the race, but maybe I can break open when it's already open. I'll have to wait for the situations and pick the right moment.
"I think everyone knows we can't take Wout to the finish, although he has already lost in the sprint after a difficult race. But it's always a risk.
Aleksandr Vlasov (Bora-Hansgrohe)
"I hope so. I'm in good shape and of course I will try.
"We need to be smart in the final and see how Sergio feels and how I feel. We will see during the race and try to play smart.
"For me it will be best to be in a select small group in the final. Maybe I will try [on Roche-aux-Faucons], why not?"
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