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Santana was born Johan Ramon Santana, and used that name throughout his life until 2003. At that time, he decided to change his name to avoid having the same name as pitching star Johan Santana. According to Ervin Santana, "I just came up with Ervin... Ervin Santana, that sounds good."
Santana was a starting pitcher for the Angels' Double-A affiliate, the Arkansas Travelers early in 2005, where he posted a 5-1 record and 2.31 ERA in 7 starts. Following an injury to Angels starting pitcher Kelvim Escobar, Santana earned a promotion. He made his first major league appearance on May 17, 2005 against the Cleveland Indians, in which he gave up the pitching version of the cycle (single, double, triple, and a home run) in just his first inning. In his second start, facing the Chicago White Sox's Jon Garland (who at the time had the best record in baseball), Santana bested Garland by pitching a complete game shutout. He gave up only 5 hits and struck out 7 for his first career victory. Santana then went on the disabled list and was sent back down to the minors to the Angels Triple-A affiliate, the Salt Lake Bees.
After Escobar's elbow problems became a recurring problem, he was placed back on the DL and Santana received his second call up to the majors. He pitched well enough to earn a spot on the playoff roster, but was initially left out of the four-man rotation. In the pivotal Game 5 of the American League Division Series of the playoffs against the New York Yankees, Angels ace Bartolo Colón went out with a shoulder injury in the second inning. Santana filled in as the long reliever, and pitched 5-1/3 innings to earn his first playoff win in his first appearance.
His short rookie season with the Angels ended with 12 wins in the regular season. In the 2006 season, he finished with a 16-8 record. After a disappointing start to the 2007 season where he went 5-11 with a 6.22 ERA, he was optioned to Triple-A Salt Lake Bees on July 18, 2007. He was recalled by the Angels on August 17, 2007, and regained his spot in the starting rotation.
On April 30, 2008, Santana equaled an Angels record with a 5-0 start to the season. He joined Angels legend Frank Tanana and teammate Joe Saunders, who equaled Tanana the day before. Santana was 11-3 with a 3.34 ERA at the 2008 All-Star Break. Pitching in the 2008 MLB All-Star Game, Santana gave up a fifth inning homer to Matt Holliday of the Colorado Rockies.
On September 22, 2008, Santana pitched against the Seattle Mariners, going 8 innings allowing 5 hits, 1 earned run, and striking out 9 en route to his career-high tying 16th win of the season. On October 3, 2008, he gave up 4 runs in the first inning, 5 total in the game, to put his team behind the Boston Red Sox in Game 2 of the ALDS.
Santana started out the 2009 season on the disabled list. On his first game of the season he received a no-decision against the Boston Red Sox.
After struggling with a disappointing 8.35 ERA, The Angels placed Santana on the disabled list.
On September 28, 2009, Santana pitched a complete game shutout becoming the first pitcher in franchise history to pitch a shutout in a game to clinch the Western Division.