Since the 21st century, except for La Liga traditional top three ( Real Madrid , Barcelona, Atletico Madrid ) that advanced to Champions League knockout match:
1, Real Sociedad
2003/2004 season to reach the top 16 of the Champions League.
2, Vigo Celta
2003/2004 season to reach the top 16 of the Champions League.
3, Valencia
1999/2000 season, and 2000/2001 season reached the Champions League final.
2002/2003 seasons and 2006/2007 seasons to the quarterfinals of the Champions League.
2010/2011 season, 2012/2013 season, and 2019/2020 season reached the top 16 of the Champions League.
4, La Coruna
2000/2001 and 2001/2002 seasons to the Champions League quarter-finals.
2003/2004 season to reach the Champions League semi-finals.
5, Sevilla
2007/2008 season, 2009/2010 season, 2016/2017 season, and 2020/2021 season to reach the top 16 of the Champions League.
2017/2018 season to reach the quarterfinals of the Champions League.
6, Malaga
2012/2013 season to reach the Champions League quarter-finals.
7, Villarreal
2005/2006 seasons and 2021/2022 seasons to the semi-finals of the Champions League.
2008/2009 season to reach the quarterfinals of the Champions League.