Spain became the first nation to have five teams qualify for the Champions League group stages as Valencia beat Monaco in a qualifying play-off.
The 2001 runners-up, who have ex-Manchester United defender Phil Neville on their coaching staff, join Real Madrid, Barcelona and Atletico Madrid.
Sevilla are also in the draw after qualifying via their triumph in last season's Europa League.
The draw for the group stages will be made on Thursday.
Valencia secured their place via a 4-3 aggregate victory, despite a 2-1 defeat in France. Former Manchester City striker Alvaro Negredo scored the visitors' crucial away goal.
Sevilla's place in the 32-team group stages is a first, with Uefa introducing a Champions League place as a prize for the Europa League winners in 2014-15.
Spanish teams have won four of the last seven Champions League, with Barcelona defeating Juventus in May's final.
Spain lead Uefa's the club coefficient rankings - the system used to decide which leagues get most qualifying spots for its competitions - by a considerable margin.