Rafa Martínez started playing basketball for Basquet Manresa eventually rising from the club's junior team ranks. The team previously played in the Spanish second division LEB but was promoted to the ACB for the 1999–2000 season where on October 9, 1999, he made his professional debut in the top Spanish league against FC Barcelona. The following season he spent in the Basketball team CB Vic. After spending two years in the Valls Felix Hotel in LEB-2, he returned to the Basquet Manresa in 2003.
In 2008, Martínez joined Valencia Basket. He won the EuroCup in the 2009–10. Along with that, Martínez had the highest three-point percentage in the Liga ACBthat season. In the 2013–14 season, he won the Eurocup for the second time.
On July 8, 2020, Martínez had signed with Baxi Manresa of the Liga ACB.[3] On July 15, 2021, Baxi Manresa announced that Martínez would play one more season for the club.[4]