At twenty-two he was affected by a disease (perhaps elephantiasis) that disfigured the face. Miraculously healed, he decided to devote himself completely to the Lord as a priest. He moved to Naples, he resumed his studies and devoted himself especially to the reading of the theological writings of Thomas Aquinas. Ordained in 1587, he began his ministry by joining the Company of the Whites of Mercy, whose purpose was to assist the sick, the poor, prisoners and death convicts.
Since in the Bianchi Company was also a man with his same name, he was mistakenly delivered a letter by Giovanni Agostino Adorno and Fabrizio Caracciolo containing the invitation to join them to start a new religious congregation: the exchange of person was considered a sign of Providence and Ascanio was admitted in the number of the founders of the institute.
The three retreated to the Camaldoli hermitage of San Salvatore in Naples, where they drew out the rule of the future Congregation of Clerks Regular Minor, then the two Caracciolos went to Rome, where Pope Sixtus V gave them his approval with the bull Sacrae religionis of 1 July 1588. At Francesco's suggestion, to the classic three vows of poverty, chastity and obedience, a fourth was added: that of not accepting any ecclesiastical dignity.
On April 9, 1589 Ascanio made his solemn profession in the chapel of the company of the Whites and took the name of Francesco, for his great devotion to Saint Francis of Assisi. After the death of Adorno, who until then had been the group leader, Francesco Caracciolo was elected superior general of the order, and gave a significant boost to the spread of his followers both in Italy and abroad, founding in 1594 the first houses in Spain. He left the government of the Clerics Regular Minor (which in his honor became known as Caracciolini) in 1607 and would not hold any office in the order.
In 1608, with his brother Antonio, he went on a pilgrimage to the Holy House of Loreto. Once near the sanctuary, he suddenly exclaimed: "Here's the place of my rest." Then he proceeded to Agnone, where he had been invited by the Fathers of the Oratory, who wanted to join the Clerics Regular Minor and had asked him to open a house at their church.
Taken by a violent fever, he was able to receive the last sacrament on his knees, then went into agony repeating, "Come on, let's go!", And when asked where, he replied: "To heaven, to heaven." He died on June 4 of that same year, on the eve of Corpus Christi.