Valencia

After his success at Zaragoza, the team was in need of money,as a result, Villa made his big move to one of Spanish football's heavyweights, as a new look Valencia under Quique Sánchez Flores parted with €12 million to secure his services in the summer of 2005.During his first game in a Valencia shirt, an Intertoto Cup match against Belgian outfit K.A.A. Gent, Villa scored the first goal in a game which Valencia won 2–0.He made his league début for Valencia coming on as a substitute against Real Betis in a 1–0 win on 27 August 2005.The next match would see his previous team, Real Zaragoza, leading 2–1 for the majority of the match, however, on the 81st minute, Villa came on as a late substitute for Rubén Baraja and scored the equalizer within the space of a minute, earning Valencia a point as the game ended 2–2.
On 21 September, Villa would once again save Valencia a vital point by netting a brace against Barcelona at Camp Nou, actually giving his team the lead at one point after Víctor Valdés' clearance rebounded off Villa's back and into the net.On 23 October, Villa scored the winning goal against another Spanish giant, this time Real Madrid at the Santiago Bernabéu Stadium and would once again score against Barcelona, on 12 February 2006, his one goal proving enough to secure all three points in a 1–0 victory.Villa scored a goal against Deportivo de La Coruña (at the Riazor on 4 February 2006), described as "superb" by ESPN and "his best" by Sid Lowe who went on to credit it even more pointing out he achieved it "on the turn".Hitting the ball from the half way line (50 yards out) it sailed over the keepers head and into the net.
He scored his first hat-trick for Valencia against Athletic Bilbao at San Mamés in La Liga on the 23 April 2006. Villa managed the hat-trick in just over five minutes (80th to the 85th minute) making it one of the quickest hat-tricks ever recorded. Valencia won that game 3–0.That season saw him score 25 goals in 35 league matches for Valencia, finishing one goal behind the league's top scorer Samuel Eto'o of Barcelona. Villa's goal tally that year was the best that any Valencia player had ever achieved since Edmundo Suárez over 60 years beforehand.