Hiram Mier was a squad member during the 2012 CONCACAF Olympic Qualifying Tournament and was selected as team captain. He led the Mexico team to win all of its matches including the final against Honduras, winning 2–1, in the tournament. He created a defensive doublet with Diego Reyes. Mexico qualified to the 2012 Summer Olympics after eight years, missing out on the 2008 edition.
Once again Mier was selected as team captain in this Pre-Olympic Games tournament held in France. Mexico would make it to the final against Turkey winning 3-0 with Mier also managed to score in the final. This was Mexico's first title in this competition.
Hiram Mier made the final cut for those players participating in the 2012 Summer Olyimpics held in Great Britain. Mexico would make it to the final against Brazil winning the match 2–1. Mier played an important role by demonstrating leadership and team work alongside Diego Reyes. Hiram Mier played all 6 matches.
Hiram Mier received his first call up to the Mexico national football team after 5 players tested positive for Clenbuterol. Coach Jose Manuel de la Torre called up Mier and 4 players as substitutes to compete for the Gold Cup; Mier did not make an appearance and Mexico would win the tournament final after defeating the United States 4–2. Mexico national under-23 football team
On 23 May 2011, Mier was called up to the Mexico U-22 team to participate in the 2011 Copa America, However Mexico was limited to take a team made entirely of players under age 22. Mier made his unofficial debut with the Mexico team, 4 July 2011 against Chile, playing all 90' minutes. Chile won the match 1–2. Hiram would go on and play all of the group matches in a Center-Back position disputing all 90' minutes of the matches, Mexico did not reach the knock-out stage of the tournament and was placed last in their group. Hiram officially made his debut with the Mexico national football team 31 May 2013 against Nigeria, in the Reliant Stadium, coming in for Francisco Rodríguez at half time. The match ended in a 2–2 tie for Mexico.
2013 Confederations Cup
Hiram Mier was selected by coach Jose Manuel de la Torre to dispute the Confederation Cup held in Brazil. He made his debut in the Confederations cup against Italy coming in as a substitute for Javier Aquino in the 53' minute of the match. Mier also played the full 90' minutes against Brazil and Japan playing as a Right Back.
Hiram Mier only played one 2014 World Cup qualifying match against arch rivals, United States; 10 September 2013 in the Columbus Crew Stadium in which Mexico lost 0–2. Hiram Mier was selected as one of the domestic league players to dispute the Intercontinental Play-off against New Zealand by new coach Miguel Herrera, however an injury caused by a right knee ligament rupture during a League match left him out for 7 months missing the 2014 World Cup also.