Archbishop Girolamo Prigione, who also served at diplomatic posts in El Salvador, Guatemala, Ghana and Nigeria, died in his native Diocese of Alessandria, Italy.
He played an important role in Mexico as it established relations with the Vatican in 1992, ending decades of estrangement and restrictive rules such as priests and nuns not being allowed to wear habits in public.
His role was not without controversy, however. Archbishop Prigione pursued close ties with the country's political class and promoted conservative clerics to key positions and dioceses, according to church observers.
Following the announcement of his death, the Mexican bishops' conference expressed its gratitude for the archbishop's diplomatic service to the country.
"We entrust him into the loving hands of God, our Lord and we ask that Our Lady of Guadalupe intercede for him. May he rest in peace," the bishops wrote.
Born in Castellazzo Bormida, Italy, Oct. 12, 1921, Archbishop Prigione was ordained a priest in 1944.
He began his diplomatic service at the Vatican in 1951 and went on to work at the Vatican's diplomatic posts in Italy, Great Britain, the United States and Austria. He also served as a papal delegate at the International Atomic Energy Agency in Vienna in the 1960s.
In 1968, he was named as apostolic nuncio to El Salvador and Guatemala by Blessed Paul VI. He also served as the apostolic delegate to Ghana and Nigeria before his appointment as apostolic delegate to Mexico in 1978.
Fourteen years later, St. John Paul II appointed the then-71-year-old Archbishop Prigione as Mexico's first apostolic nuncio and served until his retirement in 1997.