Caceres was established as a Diocese on 14 August 1595 alongside the Dioceses of Cebu and Nueva Segovia vy virtue of the Papal Bull Super specula militantis ecclesiae of Pope Clement VIII. The Diocese was then a suffragan of Manila, which was elevated to an Archdiocese by virtue of the same document. At that time, the diocese extended over "the provinces of Camarines and Albay as far as and including the islands of Ticao, Masbate, Burias and Catanduanes; the province of Tayabas as far as and including Lucban; and, in the contracosta of Mauban to Binangonan, Polo, Baler and Casiguran." The official name given to the ecclesiastical jurisdiction was Ecclesia Cacerensis in Indiis Orientalius or The Church of Caceres in the Oriental Indies. The name of the Diocese was taken from Ciudad de Nueva Caceres, the Spanish-era name of the City of Naga.

​

In 1706, Bishop Andres Gonzales, OP ordained the first Bicolano and second Indio Priest in the person of Don Gregorio Cabalquinto. In 1710, Fr. Miguel Robles de Covarrubias introduced the devotion to Nuestra Señora de Peñafrancia. In 1707, the Casa de Clerigos, now known as the Holy Rosary Minor Seminary, was established during the incumbency of Bishop Domingo Collantes, OP. In 1865, Bishop Francisco Gainza, OP invited the Vincentians to systematize Seminary formation and the Daughters of Charity to open the Colegio de Sta. Isabel, the first normal school for girls in the Philippines. The Seminary and the Colegio were then known as the best centers of learning outside of Manila. Bishop Gainza initiated ecclesiastical reforms and fostered closer relations with the Holy See. In 1905, Monsignor Jorge Barlin was appointed and ordained as Bishop of Caceres, become the first Filipino Bishop. Barlin prevented the growth of a nationalistic schismatic movement when he won the Supreme Court case against the Aglipayans. 

​

More than three hundred years since its foundation, the Diocese of Caceres, alongside the Archdiocese of Manila, gave birth to the Diocese of Lipa in 1910; from which, later came the Dioceses of Lucena, San Pablo and Gumaca, and the Prelature of Infanta. As such, Caceres became a purely Bicol territory.

​

On 29 June 1951, Pope Pius XII elevated Caceres to an Archdiocese through the Papal Bull Quo in Philippina Republica. On the same date and through the same document, two suffragan Dioceses were created: Legazpi and Sorsogon. The latter comprised of the civil Provinces of Sorsogon and Masbate, while the former comprised of the civil Provinces of Albay and Catanduanes. This left the new Archdiocese to be comprised by what was referred to as Ambos Camarines or the civil Provinces of Camarines Norte and Camarines Sur.

​

On 23 March 1968, the Diocese of Masbate was created, separating it from the Diocese of Sorsogon. It is comprised by the entire civil Province of Masbate. On 27 May 1974, the Diocese of Virac was created, separating it from the Diocese of Legazpi. It is comprised by the entire civil Province and Island of Catanduanes. On 01 September 1974, the Diocese of Daet was also created, separating it from the Archdiocese of Caceres. It is comprised by the entire civil Province of Camarines Norte. On 19 March 1990, upon the petition of then-Archbishop Leonardo Z. Legaspi, OP, the then-first Congressional District of the Province of Camarines Sur was separated from the Archdiocese of Caceres, forming the Prelature of Libmanan. On 25 March 2009, Libmanan was elevated into a Diocese.

​

Today, the Archdiocese of Caceres has six suffragan Dioceses, namely: Legazpi, Sorsogon, Masbate, Virac, Daet and Libmanan. It is comprised of the Third, Fourth and Fifth Congressional Districts of Camarines Sur and the Municipality of Gainza. The Archdiocese currently has 93 Parishes, 01 Minor Basilica, 01 National Shrine, and 23 Congregations of Religious Men and Women. As of 2021, it has a population of 1,903,279, representing 97.5% of the 1,952,544 individuals in the aforementioned territory.