With Gerard Pique suspended for the contest and Javier Mascherano injured, Vermaelen has been given just his second start of the campaign alongside Samuel Umtiti, with his only previous start coming in the Copa del Rey against third-tier side Real Murcia in October.
The Belgium international defender's last Liga appearance came in March 2016 in a win over Getafe. His last start came in January of the same year, as the defender spent last season on loan in Serie A with Roma.
Sunday's match marks just his 12th Liga appearance in total, though Barca have never lost when the former Arsenal man has been on the pitch.
The rest of the line-up is as expected, with Nelson Semedo, Umtiti and Jordi Alba joining Vermaelen on the back line.
The midfield will be Sergio Busquets, Ivan Rakitic and Andres Iniesta while the forward three will be Suarez and Paulinho along with Messi.
Barca kick-off four points clear of Valencia at the top of the table, with both teams still unbeaten in the Liga this season.
Barcelona line-up: ter Stegen; Semedo, Umtiti, Vermaelen, Alba; Busquets, Rakatic, Iniesta; Messi, Suarez, Paulinho
Valencia line-up: Neto; Montoya, Paulista, Garay, Gaya; Carlos Soler, Parejo, Kondogbia, Guedes; Rodrigo, Zaza