Widely considered one of the greatest defensive catchers of all time for his blocking ability and his caught-stealing percentage, Molina won nine Rawlings Gold Gloves and six Fielding Bible Awards.

His father was an amateur second baseman and the all-time hits leader in Puerto Rican baseball, and his two older brothers, Bengie and José, also developed into standout defensive catchers with lengthy MLB careers.

The Cardinals' fourth-round selection in the 2000 MLB draft, Molina entered the major leagues in the 2004 season and quickly showed one of the strongest and most accurate arms in the game.

Over his career, he earned a reputation as a team leader, eventually formulating pregame plans to handle opposing hitters, including pitching strategies and fielder positioning.

When Hurricane Maria ravaged the island of Puerto Rico in September 2017, Molina began relief efforts for victims of the catastrophe, consequently receiving the Roberto Clemente Award in 2018.

The all-time hits leader in Liga de Béisbol Profesional Roberto Clemente (or Doble-A Beísbol) history, the elder Molina delivered a .320 career batting average and gained election to the Puerto Rican baseball hall of fame in 2002.

Molina's two older brothers, Bengie and José, also developed into distinguished defensive catchers with lengthy careers in Major League Baseball (MLB), and each of the three won at least one World Series championship.

He observed that Molina's skills closely resembled that of both his older brothers—both accomplished major league catchers[9][10]—and decided that his defense was "polished" enough to be considered more advanced than most high schoolers in the United States.

He put on a spectacle at Riverfront Stadium with his arm and bat that grabbed the attention of executives, scouts, and prominent former Reds players, including Johnny Bench and Bob Boone.

Ricketts, who had a reputation for becoming upset when minor league catchers allowed balls to bounce between their legs, removed Molina from the game and drove him to the batting cage.

On the play, the center fielder, Mike Cameron started towards the outfield wall based on Molina's full swing, not immediately realizing that he had made only partial contact because of the broken bat.

[17] Three weeks later, on August 29, the Cardinals beat the Pittsburgh Pirates 6–4, thanks in part to two plays in which Molina tagged out the runner at home plate, including a collision with Ty Wigginton.

[13] Even as his bat languished, Molina's defense was instrumental in propelling the Cardinals to the National League Central division crown in a season heavily marred by injuries for the team.

[34] In the bottom of the ninth, rookie pitcher Adam Wainwright – filling in as emergency closer – found himself in a two-out, bases-loaded situation against center fielder Carlos Beltrán, who had already homered three times in the NLCS.

[43] After a home plate collision with Eric Bruntlett on June 15 against the Philadelphia Phillies in the ninth inning, Molina sustained head and neck injuries and was removed from the field on a stretcher.

[53] Following the All-Star break on July 18, Molina's four hits and Albert Pujols' two home runs helped cap Chris Carpenter's 6–1 victory over the Diamondbacks, who pitched around nine runners on base in eight innings.

[87] In a game against Pittsburgh at PNC Park on August 28, he sustained head, neck and back injuries – although no concussion – in a second-inning home plate collision with second baseman Josh Harrison.

[87] From a historic perspective, Fangraphs' Dave Cameron noted that Molina's combination of offensive productivity and interception of base runners in 2012 was one of the rarest performances in history.

Following his 2012 fourth-place MVP finish, his 2013 in-season jersey sales rose to third place, just after Posey and retiring New York Yankees closer Mariano Rivera, according to a July 11 report.

[101] A magnetic resonance image (MRI) indicated inflammation but no structural damage, so the knee was drained of excess fluid buildup and Molina was given a cortisone injection.

A continuously evolving core exceeded expectations by filling in for 52 games started, 36 wins, and five saves and Molina was credited with their success in a large part due to his pitch-calling skills and aptness to guide.

Molina threw out pinch runner Josh Harrison attempting to steal second base in the eighth inning to help the Cardinals preserve a 2–1 lead.

[126] Molina stayed in the lead and won the vote as the starting catcher in the All-Star Game at Target Field in Minneapolis, Minnesota, his sixth consecutive appearance.

[146] In the annual Baseball America Toolbox Awards, managers and coaches around the National League rated Molina as both the "Best hit and run artist" and "Best defensive catcher" in the NL.

[157] Molina's ninth-inning, RBI double, tied the July 27 game against the New York Mets at 4−4, ending Jeurys Familia's consecutive-saves streak of 52, the third-longest in major league history.

The appointment created some controversy in Puerto Rico after the resignation of team general manager Eduardo Pérez, who had reportedly sought to name Astros bench coach Joe Espada to the position.

[225] At the tournament, Molina managed Puerto Rico to eight perfect innings against Israel, as well as a 5-2 upset victory over the Dominican Republic to decide which team moved on to the knockout stage.

[227] The winner of eight consecutive Gold Gloves,[228] Molina was widely praised for his preparation, defense and leadership, not just of the pitching staff, but also of the entire team, even from Johnny Bench.

Over time, with assistance of teammates such as Pujols, Molina found his comfortable stance, sounder mechanics and adopted a line-drive style of swing that eliminated the dip and helped him hit fastballs with more authority.

[262] Spurred by absences from autograph shows for which he was paid to appear, Steiner Sports Marketing filed a lawsuit for $175,000 against Molina in the New York state supreme court in Manhattan on October 2, 2009.