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The Roman Catholic Archdiocese of Mexico is the metropolitan diocese of Mexico City. It was elevated on February 12, 1546.

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Francisco de Aguiar y Seijas y Ulloa was a Spanish cleric and bishop, notable as bishop of Michoacán and archbishop of Mexico.

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Ernesto Corripio y Ahumada was a cardinal of the Roman Catholic Church. He was Archbishop of Mexico in Mexico City (1977–1994) and was Primate of Mexico. In the consistory of June 30, 1979 in Vatican City Pope John Paul II created him Cardinal Priest of the titular church of Mary Immaculate of Tiburtino.

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Payo Enríquez de Rivera y Manrique, O.E.S.A., was a Spanish Augustinian friar who served as the Bishop of Guatemala (1657–67), Archbishop of Mexico (1668–1681) and Viceroy of New Spain.

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Fray García Guerra, OP, archbishop of Mexico and viceroy of New Spain. He held the former office from December 3, 1607 and the latter from June 19, 1611. He still occupied both offices at the time of his death in 1612.

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Pelagio Antonio de Labastida y Dávalos was a Mexican Roman Catholic prelate, lawyer and doctor of canon law, and politician. He was a member of the imperial regency that invited Maximilian of Austria to accept the throne of Mexico.

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Francisco Javier de Lizana y Beaumont was bishop of Mexico and, from July 19, 1809 to May 8, 1810, viceroy of New Spain.

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Francisco Antonio de Lorenzana y Butrón was a Catholic Cardinal, who had also earlier served as Archbishop of Mexico.

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Francisco de Manso Zuñiga y Sola was a Roman Catholic prelate who served as Archbishop of Burgos (1640–1655), Archbishop of Cartagena (1637–1640), and as Archbishop of Mexico (1627–1634).

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Miguel Darío Miranda y Gómez was a Mexican Cardinal of the Roman Catholic Church. He served as Archbishop of Mexico City from 1956 to 1977, and was elevated to the cardinalate in 1969.

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Alonso de Montúfar y Bravo de Lagunas, O.P., was a Spanish Dominican friar and prelate of the Catholic Church, who ruled as the second Archbishop of Mexico from 1551 to his death in 1572. He approved and promoted the devotion to Our Lady of Guadalupe that arose during his reign.

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Pedro Moya de Contreras was a prelate and colonial administrator who held the three highest offices in the Spanish colony of New Spain, namely inquisitor general, Archbishop of Mexico, and Viceroy of Mexico, September 25, 1584 – October 17, 1585. He was the 6th Viceroy, governing from September 25, 1584, to October 16, 1585. During this interval he held all three positions.

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Dr. Alonso Núñez de Haro y Peralta was archbishop of Mexico from September 12, 1772, to May 26, 1800, and viceroy of New Spain from May 8, 1787, to August 16, 1787.

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Don Juan Ortega y Montañés was a Roman Catholic bishop and colonial administrator in Guatemala and New Spain. He was successively bishop of Durango, of Guatemala and of Michoacán, and then archbishop of Mexico. He also served as interim viceroy of New Spain from February 27, 1696 to December 18, 1696 and again from November 4, 1701 to November 27, 1702.

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Carlos Aguiar Retes is a Mexican cardinal of the Roman Catholic Church who serves as the Archbishop of Mexico City. He has served as an officer of the Mexican Episcopal Conference and the Latin American Episcopal Conference (CELAM) and been president of both. He helped draft the landmark mission statement CELAM issued at the close of its 2007 conference in Aparecida. He is the former archbishop of Tlalnepantla, and before that, served as the Bishop of Texcoco. David Agren of the Catholic News Service calls him a "longtime ally" of Pope Francis who combines "intellectual finesse with a pastoral passion".

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Norberto Rivera Carrera is a Mexican prelate of the Roman Catholic Church. He was the Archbishop of Mexico City from 1995 to 2017. He was made a cardinal in 1998.

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Feliciano de la Vega Padilla was a Roman Catholic prelate who served as Archbishop of Mexico (1638–1640), Bishop of La Paz (1633–1638), and Bishop of Popayán (1631–1633).

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Juan Antonio de Vizarrón y Eguiarreta was archbishop of Mexico from March 21, 1731 to January 25, 1747 and Spanish viceroy of New Spain from March 17, 1734 to August 17, 1740.

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Don Juan de Zumárraga y Arrazola was a Spanish Basque Franciscan prelate and first bishop of Mexico. He wrote Doctrina breve, the first book published in the Western hemisphere, printed in Mexico City in 1539.