A total of 20 teams competed in the league: 17 sides from the 2012–13 season and three promoted from the 2012–13 Serie B campaign.

Palermo, Pescara and Siena were each demoted from the top flight.

They were replaced by Serie B champion Sassuolo, runner-up Hellas Verona and play-off winner Livorno.

Hellas Verona returned to Serie A after an 11-year absence, Livorno after four seasons and this season marked Sassuolo's Serie A debut.

For the first time in the competition's history, there were five derbies among teams from the same city: Milan (Internazionale and Milan), Turin (Juventus and Torino), Rome (Lazio and Roma), Genoa (Genoa and Sampdoria), and Verona (Chievo and Hellas Verona).