Barca struggled away from the Nou Camp in Europe last term, scoring just once in three group stage matches and surrendering a 4-1 lead against Roma on a dreadful night at the Stadio Olimpico to exit at the quarter-final stage.
But they put four goals past Tottenham at Wembley last month and second-half strikes from Lionel Messi and Gerard Pique proved enough for all three points against PSV Eindhoven at the Philips Stadion, despite Luuk De Jong setting up a tense finale.
In truth Barca rode their luck as Gaston Pereiro, De Jong and Denzel Dumfries were all denied by the frame of the goal in the opening 45 minutes, but Valverde is pleased with their progress after the 2-1 win.
The Barca head coach said in quotes on his club's official website: "We're so happy to have mathematically topped the group.
"Considering how much we have struggled away from home in recent years and found it hard to score goals, I'm especially pleased to have got two wins and a draw this year.
"PSV played well. They were very lively on the counter-attack and the balls we lost meant they were able to get into dangerous positions and even hit the woodwork a few times. 'It was a hard place to play at. But the more the game progressed the more chances we were able to create."