A review of the Copa del Rey ties on Tuesday night as Barcelona and Valencia both earned away wins at lower-league opposition.
Barcelona got their title defence off to a flying start with a 3-0 win away to third-tier Alaves.
David Villa fired Barca ahead on 40 minutes when his strike crashed off the crossbar and over the line before Andres Iniesta added breathing space shortly after half-time.
Cesc Fabregas ensured Barca would take a healthy advantage to the Nou Camp in next month's return leg with a third late on.
Valencia also beat Segunda Division B opposition as they cast Llagostera aside 2-0 at Estadi Municipal.
After the hosts initially held firm, Jonas headed in from a Daniel Parejo cross on the stroke of half-time.
Nelson Valdez managed to get on the end of a Parejo delivery to wrap up the scoring on 68 minutes.