[13] In 2010 he joined the Russian Team Katusha, which guaranteed him a position at the Tour de France and a leading role in certain races throughout the season.

[16] In 2011 he won a stage at the Tour of the Basque Country and finished second behind Philippe Gilbert at both the Amstel Gold Race and La Flèche Wallonne.

[17] He started the second half of the season by finishing fourth at the Clásica de San Sebastián and winning the overall classification and a stage at the Vuelta a Burgos.

On 18 April 2012, he won La Flèche Wallonne in Belgium with a superb climb on the Mur de Huy and finished second in the Tour of the Basque Country.

[19] On the Vuelta a España, Rodríguez almost took the win on stage 3, but Alejandro Valverde popped up on his right to steal the victory in a photo finish, and snatched the red jersey.

[21] He took the sixth stage, the majority of it was flat but the riders had to tackle with two Category 3 climbs near the conclusion, the line being situated atop the last one, the Fuerte del Rapitán in Jaca.

With 500 m (1,600 ft) remaining, Chris Froome launched an attack which only Rodríguez could follow, before passing the Team Sky rider and grabbing both the victory and the twelve-second time bonus.

[22] The scenario repeated itself on stage 12, where Rodríguez escaped from the lead group with Alberto Contador on the final difficulty of the day, the very steep climb Mirador de Ézaro.

[25] Despite his attacks on the penultimate stage in the steep climb of Bola del Mondo, Rodríguez could not improve his third placing although he gained some time on Contador.

[26] Rodríguez went to Italy to compete in the Giro di Lombardia, where he had the opportunity to take the first place in the 2012 UCI World Tour detained by Bradley Wiggins.

However, Rodríguez managed to move into a podium position in the final general classification after gaining over a minute over Alberto Contador and Roman Kreuziger.

[29] After the Tour de France, he took a long break and then came as the leader of Team Katusha at the start of the Vuelta a España, a race he twice finished on the podium in the past.

One of the favorites at the start of the race, Rodríguez won the 19th stage and finished fourth in the overall classification, more than three minutes behind winner Chris Horner.

[30] Afterwards, he raced the World Championships, where he came short of winning the rainbow jersey, after being caught by eventual winner Rui Costa in the last kilometer.

One week later, Rodríguez took revenge for his defeat at the Giro di Lombardia, winning for the second consecutive year with a perfectly timed attack on the Villa Vergano climb.

He had his first win of the season on a mountainous third stage of the Tour of the Basque Country, outsprinting Nairo Quintana and Sergio Henao after a descent in Zumarraga.

[44] His stated aim for the Tour de France was to achieve a top ten finish in the general classification, and his bid started strongly, holding third place overall after the first stage in the Pyrenees.

[46] Subsequently, his performances dipped somewhat in the second week of the race, dropping him down to 12th in the general classification following a couple of bad days.

After the race he told the media that the Clásica was his final competition in Spain, ruling out participation in the Vuelta a España, whilst Katusha directeur sportif Xavier Florencio described Rodríguez's ride in San Sebastián as being his last for the team.

[48] However, in September it was reported that Katusha would enter Rodríguez into the Trittico di Autunno classics and the Abu Dhabi Tour before the end of the year, with his contract with the team not expiring until 31 December.