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Alfredo Pacini was born in Capannori and studied at the seminary in Lucca before being ordained to the priesthood on 25 July 1913. He then did pastoral work in the Archdiocese of Lucca and taught at its seminary until 1915, when he became a military chaplain during World War I. After resuming his work in Lucca, Pacini was raised to the rank of Honorary Chamberlain of His Holiness on 8 October 1924. He served as secretary (1924-1928) and auditor (1928-1933) of the nunciature to Yugoslavia. From 1935 to 1944, he was auditor of the Polish nunciature. He became Domestic Prelate of His Holiness on 3 September 1935 and counselor of the nunciature to France in 1944.
On 23 April 1946, Pacini was appointed Nuncio to Haiti and Santo Domingo and Titular Archbishop of Germia by Pope Pius XII. He received his episcopal consecration on the following 11 June from Archbishop Angelo Roncalli, with Archbishop Louis Le Hunsec, CSSP, and Bishop Stanislas Courbe serving as co-consecrators, in Paris.