The 31-year-old had his best Grand Tour result in the Spanish race in 2011 when he finished just off the podium behind Juan Jose Cobo and Sky duo Chris Froome and Bradley Wiggins.
It will be the first time Mollema has competed in the Vuelta since 2013, and the team is going in with modest ambitions for the overall, with directeur sportif Yaroslav Popovych aiming for a top five.
"We are coming to the Vuelta with big goals, but goals that we believe we have a very good chance of achieving," Popovych said in the team announcement.
"On the one hand we will try to hunt for stage victories, in the flat stages with Giacomo Nizzolo, who has showed in the recent Tour of Poland that he his in good shape. Then, we also have Gianluca Brambilla and Fabio Felline who will show their full support to Bauke but who can also go for stage wins from a breakaway. And we have Matthias Brändle who can do really well in the prologue and the TT.
"On the other hand we have Bauke Mollema, who came with great legs from the Tour de France, finishing 2nd in 'his' race, the Clásica Ciclista San Sebastián and who is aiming for the overall. The whole team will be there to protect him and to bring him to Madrid in the perfect position and as highly ranked as possible. We strongly believe he can attain a top five if all goes well."
Markel Irizar, Kiel Reijnen and Grand Tour debutente Nicola Conci round out the team.
"I see a lot of opportunities for us in this Vuelta. We have a very strong team assembled and it will be a very exciting three weeks for all of us."
Trek-Segafredo for the Vuelta a España 2018: Gianluca Brambilla, Matthias Brändle, Nicola Conci, Fabio Felline, Markel Irizar, Bauke Mollema, Giacomo Nizzolo, Kiel Reijnen.