Villarreal have been relegated after defeat to Atletico Madrid.
Villarreal's 12-year stay in the top flight came to a shock end on Sunday night as Radamel Falcao's late goal for Atletico Madrid sent them down to the Segunda Division.
The Yellow Submarine, who finished fourth last season, seemed set to survive as they withstood a second-half onslaught from the Europa League winners.
However, Falcao's 88th-minute header from Diego's corner, allied to victories elsewhere for Rayo Vallecano and Real Zaragoza, meant it was Miguel Angel Lotina's side who join Sporting Gijon and Racing Santander in the bottom three.