The Liga title challengers go into the clash on the back of a 3-2 win at Atletico Madrid on Wednesday which secured a 4-2 aggregate triumph and a place in the Copa del Rey semi-finals.
Barca now come up against opposition in a rich vein of form, as Villarreal have not lost any of their previous 18 matches in all competitions - with their last defeat coming at FC Zurich in a November UEFA Europa League encounter.
The odds will be stacked against Marcelino Garcia Toral's side, though, having emerged victorious from only one of their last 13 trips to Camp Nou and Xavi is determined to end the visitors' long-unbeaten run.
"Villarreal are on a long run of games unbeaten," he told reporters.
"It will be a very difficult tie for us. Maybe we are favourites, but we have to make good on that.
"We are happy with how we are physically, happy with what we are doing. Everything in this place depends on the result, all of the analysis.
"We were not so bad before, nor are we so good now. But we are on a good path and that benefits the club, the group."
Villarreal's fine run of form has seen them emerge as serious contenders for a UEFA Champions League place and they sit just three points behind fourth-placed Valencia.
A 3-1 home defeat by Nuno Espirito Santo's side on November 2 was Villarreal's most recent reverse in the league, with their charge up the table beginning shortly after that setback.
Villarreal secured a Copa semi-final berth on Thursday for the first time by overcoming Getafe to set up a two-legged tie against Luis Enrique's side.
Marcelino will expect his men to adjust their focus back to La Liga immediately and in Joel Campbell – a loan arrival from Arsenal as part of Gabriel Paulista's switch to the Premier League club – they have a forward looking to prove a point.
"I am ready to work hard and hopefully things turn out well," he is quoted as saying by AS. "My head is at Villarreal and I'm determined to prove my worth here."
Marcelino does find himself a man short ahead of the trip, however, as defender Eric Bailly - another new signing this week - is still away on Africa Cup of Nations duty with Ivory Coast, so Chechu Dorado could make only his fourth league appearance of the season.
Barcelona have almost a full squad to pick from, with Douglas and Thomas Vermaelen the only two set to miss out.
