The coverage will begin on Sunday with Levante hosting third place Real Madrid.
Weekly matches will be shown, along with a midweek highlights programme including games from the likes of Barcelona and Atletico Madrid.
The coverage will be on ITV4 until the end of the season in May.
Niall Sloane, ITV Director of Sport, said: “This is good news for football fans who will be able to see on free to air television some of the world’s best players in action for some of the world’s biggest clubs in a league known for its high levels of skill and entertainment from now until the end of the season.”
The deal comes after ITV also signed a deal with American boxing advisor Al Haymon and his Premier Boxing Champions.
ITV has aired US fights on ITV4, including Manny Pacquiao vs Adrien Broner.
While they launch their first pay-per-view fight of 2019 tomorrow with James DeGale and Chris Eubank Jr fighting on ITV Box Office.
La Liga will return to TV for the first time since Sky Sports lost the rights to streaming service Eleven Sports at the start of the season.
Eleven sports also had the rights to Serie A games – but were forced to sell the rights to Premier Sports.
The Leeds-based subscription service has also been forced to relinquish its rights to Dutch league games following the end of its partnership with management company IMG.
Their split with IMG also meant their proposed deal to air UFC coverage was scrapped with BT Sports maintaining the octagon rights.
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