In the first meeting between these sides since last year's Copa del Rey final, it was once again a win for Barcelona, who set up with Aleix Vidal on the right wing and Iniesta behind Lionel Messi, with new signing Ousmane Dembélé not yet ready to make his Barca debut.
The first half with the visitors having plenty of the ball and most of the action occurred in the Alavés half, but both sides had chances to break the deadlock. Pacheco made a number of routine saves from efforts from Deulofeu, Messi and Iniesta and Ter Stegen was out quickly to block a shot from Sobrino, who had raced away from Pique.
Barcelona's best chance of the half fell to Lionel Messi from the penalty spot after Rodrigo Ely hauled down Gerard Pique in the box and picked up a yellow card in the process. But the Argentinian fluffed his lines as Pacheco guessed correctly and got down smartly to his right to palm the penalty away for a corner.
The sides went in at half time all square, with Barcelona the more frustrated not to be ahead.
Alavés started the second half brightly as Ibai Gomez broke down the left but his cross just evaded the outstretched Rubén Sobrino. However, it was Ernesto Valverde's side who broke the deadlock on the 55 minute mark, as Jordi Alba worked it to Lionel Messi in the centre of the box, who took a touch and fired it past Pacheco, with the keeper wrong-footed following a slight deflection.
Barcelona then extended their lead 11 minutes later, with the Alavés defenders the architects of their own downfall. Alexis failed to clear the ball on the edge of the box and Alcacer pounced, heading the ball in Messi's direction, and the Argentinian rifled a shot into the bottom right corner of the net.
Messi then came within inches of a hat-trick as his effort crashed against the bar following nice work from Alcacer.
The Catalan side managed to see out the rest of the game with relative ease as the home side failed to create any guilt-edged chances following Messi's brace.
Brazilian midfielder Paulinho was able to make his Barcelona debut, after signing from Guangzhou Evergrande for €40 million, as he replaced Andres Iniesta in the final few minutes.
The result leaves Alavés still in search for their first points of the season and extends Ernesto Valverde's winning start in the league.