Illes Balears–Banesto, later Movistar Team (2005–2012)

He was also one of the best climbers on the Movistar Team, Arroyo's team from 2005 to 2012, along with the team leader Alejandro Valverde. After Valverde crashed in the first week of the 2006 Tour de France, Arroyo was made team leader, until Óscar Pereiro claimed the leader's yellow jersey. Arroyo then helped to protect Pereiro in the mountain climbs and ensure his overall victory.

Arroyo's biggest win to that point was Stage 19 of the 2008 Vuelta a España. Prior to that, his only victories came at the 2004 Volta a Portugal, where he won two stages, the mountains classification and the young rider classification.

In the 2010 Giro d'Italia, Arroyo wore the pink jersey as race leader for five days. He was part of a fortunate breakaway in stage 11 of that race that took over 13 minutes from the race's overall favourites, and claimed the jersey three days later on a mountain stage. He kept it through two mountain stages and the climbing time trial to Kronplatz, but lost it to eventual Giro champion Ivan Basso in stage 19. He finished the race second overall, in the process proving himself to be one of the best descenders in the peloton.

Grand Tour general classification results timeline

Grand Tour	2005	2006	2007	2008	2009	2010	2011	2012	2013	2014	2015	2016	2017
Giro d'Italia	—	—	10	—	8	2	13	—	—	—	—	—	—
Tour de France	53	19	12	29	66	—	34	—	—	—	—	—	—
Vuelta a España	—	19	—	17	—	24	—	—	13	20	12	122	89