The Colombian has won three individual stages of the event throughout his career, while has also finished top of the General Classification at the 2014 Giro d'Italia and the 2016 Vuelta a Espana.
After racing with Movistar between 2012 and 2019, it was announced that he would move to the French team Arkea-Samsic in the 2020 season but will be able to compete for his third Grand Tour.
Quintana will also be racing alongside Warren Barguil, a climb specialist who won the mountains classification in 2017 after winning two stages.
"Quintana-Barguil, the ticket looks great for a mountainous Tour!" said race organiser Christian Prudhomme.
Quintana moved to Arkea-Samsic from Movistar alongside his brother Dayer and countryman Winner Anacona.