Alexandre Angélique de Talleyrand-Périgord attended the Jesuit school of La Flèche en Sarthe.
He was elevated to the Archbishopric of Reims on October 27, 1777 and became Abbot commendatory of the abbey Notre-Dame de Cercamp from 1777 to 1789.
After the Civil Constitution of the Clergy, he emigrated in 1790 and stayed successively in Aix-la-Chapelle, Weimar and Brunswick.
In 1801, he refused to submit to the Concordat between the Pope and Napoleon Bonaparte and did not resign his position as Archbishop of Reims.
In 1808, Louis appointed him Grand Almoner, a position he would continue to occupy after the Restoration and until his death.