The Brazilian's long range strike proved to be the difference between the league pace setters and Los Che, who are yet to taste victory in 2012-13
Adriano's goal decided matters early in the first half, with the Brazilian finding the net through a glorious long range effort that proved to be the only goal of the evening at Camp Nou.
Seeking a third straight Liga victory after convincing wins over Real Sociedad and Osasuna, Barcelona started brightly and soon settled into their characteristic possession game, constantly probing around the Valencia box.
Pedro was one of the first to threaten Diego Alves in the away goal, expertly turning Victor Ruiz before forcing a decent save out of the goalkeeper.
Despite seeing little of the ball during the first half, it was Los Che who almost opened the scoring in the opening minutes.
Roberto Soldado took advantage of slack marking from Gerardo Pique to release a shot from distance, but the striker saw his effort curl just wide of the post.
At the other end Alves was at full stretch to deny Messi a headed strike, but the Brazilian was powerless to stop the Blaugrana hitting home with 23 minutes on the clock.
Vindicating Tito Vilanova's decision to put him ahead of Jordi Alba against the youngster's old club, Adriano smashed home a glorious effort that left Alves with no chance.
The full-back was given room after picking the ball up from a short corner, and with his right foot released a bomb that settled in the left hand corner of the net.
Cesc Fabregas should have doubled the advantage seconds later when he was left clear thanks to unselfish play from Lionel Messi, but his chipped effort brushed the post and went wide.
Valencia saw themselves pegged further and further back in their own half, at times defending with seven men behind the ball as the Liga runners-up dominated possession around the Che penalty area.
There were isolated moments of positivity from the visitors; Soldado was livid with team-mate Sofian Feghouli when the Algerian, with players up in support, decided to take the shot on himself from out wide and blazed harmlessly over the bar.
Having held Real Madrid to a draw in the Primera Division opener, however, the visitors went into half time needing to raise their game if they wanted to take anything away from this encounter.
The return of both teams to the pitch after the interval did indeed coincide with a more proactive, attacking Valencia, who looked more willing to take the initiative and not simply wait for a mistake from their rivals.
But despite enjoying a little more of the ball, clear cut chances were lacking for the visitors who could not find a way past Pique and Javier Mascherano - with the best opportunities continuing to go the way of the Blaugrana.
Fabregas had another chance to score when he blazed over the bar with the goal at his mercy, after good work from Alexis Sanchez.
Mauricio Pellegrino's men thought they had restored parity on the hour, when Victor Ruiz headed home a corner at the far post taking advantage of careless home defending. But his joy soon turned to despair when that effort was ruled out for a narrow offside.
The introduction of Andres Iniesta provoked a rousing ovation from the Camp Nou faithful as they saluted the newly crowned Best Player in Europe and his entry seemed also to lift his team-mates as they resumed control of the game.
There was no way through a dogged defensive effort from the away team, however, and the Catalans were ultimately happy to play out the last minutes and stroll to a 1-0 victory.
The win means Barca maintain their 100 per cent start to the season, as well as their place at the top of the table. The club lie two points clear of nearest rivals Mallorca, Rayo Vallecano and Malaga, while winless Valencia sit a lowly 17th after the first three games.