[2] A total of 22 teams contested the league, including 15 sides from the 2012–13 season, four promoted from the 2012–13 Segunda División B and three relegated from the 2012–13 La Liga.

[7] The teams which had been relegated from the Segunda División the previous season were Guadalajara, Racing Santander, Huesca and Xerez.

[14][15] Guadalajara was relegated to Segunda División B administratively after irregularities detected in the capital increase made the previous summer for conversion to a Sociedad Anónima Deportiva.

[16] Murcia remained in Segunda after the relegation administratively of Guadalajara, however RFEF didn't recognize the unilateral sanction by LFP[17] and the relegated or saved team was disputed between Guadalajara and Murcia until Spanish sports jurisdictional body, the CEDD (part of CSD), would make a resolution.

[18] CEDD ruled refusing the precautionary suspension of Guadalajara relegation, whereby Murcia remained in Segunda.

In case of a draw after the overtime in the second leg, there will not be a penalty shoot-out, and the best positioned team in the league table directly passes to the next round.