After his education at the Seminary of Santa Fe was Antonio there on 23 March 1912 dedicated priest . In the period 1912-1934 he was mainly engaged in pastoral work. He was active in the Catholic action in Argentina. Also, he taught at the Seminary of Santa Fe.
On 13 september 1934 was Bishop Antonio to first of the newly created diocese of Rosario chosen.  his ordination followed on 17 March 1935 and was carried out by Filippo Cortesi, assisted by the nuntius in Argentina, Nicolás fasolino, Archbishop of Santa Fe.
During the consistory of 18 February 1946 was created by Antonio Pope Pius XII to cardinal-priest taking him the title Church San Lorenzo in Panisperna was assigned. In that period he offered on behalf of the Argentine Government to the Vatican to provide asylum to war criminals from nazi Germany (see also Rats line), which in the Vatican were hiding.   after the detection and kidnapping of Adolf Eichmann on May 11, 1960 from Argentina left Antonio 23 december 1960 on Eichmann fled to Argentina, which would be to seek forgiveness, something the duty of every Christian would be able to provide that. 
On behalf of the Pope he acted as papal legate at the Congress in Argentina Maria (1954), the Congress of Catholic education in La Paz (1948). Also, he participated in the first General Conference of the episcopate of Latin America in Rio de Janeiro (1955).
On 15 August 1959, he was appointed Archbishop of Buenos Aires, followed on 14 december as military ordinariate of Argentina. In the 1960s with the Argentine military who openly sympathised Antonio bright occurred against Communist movements in the country. For the book Le Marxism-léninisme by Jean Ousset Antonio wrote the foreword. In the book the writer claimed that Marxism could only be fought by "a deep-seated faith, an unlimited obedience to the Holy Father, and a thorough knowledge of the doctrines of the Church". 
Antonio took part in the conclaves of 1958 and 1963, but due to its age-in accordance with the motu proprio 'Ingravescentem Ætatem of Pope Paul VI -he was from 1969 no longer vote for a possible next conclave.As a result, he is not taking part in the two conclaves of 1978.
On 22 april 1975 Antonio decided to resign from his Archdiocese. Antonio Caggiano died at the age of 90 and was buried in the Cathedral of Buenos Aires.