He quickly opened up a significant gap on those behind and started the Cote de Saint Nicolas with a clear gap in between himself and a chase group of Maxim Iglinskiy (Astana) and Joaquim Rodriguez (Katusha).
However the gap was quickly whittled down when Iglinskiy dropped Rodriguez, and as the Astana rider crested the top of the climb the gap was timed at seven seconds. The inevitable catch was made just before the flamme rouge, before Iglinskiy stormed to take the win by 21 seconds.
As Iglinskiy celebrated at the finish, his teammates amongst the first to congratulate him, Nibali was left alone and isolated, the mere presence of an Italian television crew for immediate company as he stopped his bike and fell over his handlebars.
"I did a good attack but because there was a lot of wind coming onto the Saint-Nicolas, it wore me out. I really believed I could do it, but when I saw Iglinskiy coming up to me, I tried to stay on his wheel," he said.
"I attacked myself on La Roche aux Faucons because I wanted to make a decent move, and it would have been hard to make a selection on the Saint-Nicolas because everybody was still up there. We would all have been up there waiting. I was just missing a little bit in the end,"
Nibali was quick to praise the Kazak rider, who in overhauling the Italian before the line, had secured the biggest win of his career.
"He's always been an excellent rider, but maybe if a Gilbert had come past me, I would have been happier."
Tactically, Nibali cannot be criticised. He peppered the opposition with attacks on the Cote de la Roche aux Faucons, before pressing home his advantage on the descent.
"There's not much to reflect on, because I certainly did a good race. I really wanted to do well here in Liège this week. I didn't get anything wrong today, I was just missing something in my legs in the finale."
"There's a bit of disappointment of course, but it's not like I'm going to stop here."
"I tried to hang on when I heard that Iglinskiy was chasing me, maybe it would have been better to have sat up and then tried to play my hand in the sprint."