Saint Vincent Pallotti had a maternal aunt, Marta De Rossi, who became a Poor Clare nun in 1790, taking the name Sr. Rita. During the occupation of Rome by Napoleon's troops (1809-1814), his government suppressed religious communities and, like many Poor Clare nuns from various convents, Sr. Rita may have found refuge for some time in their convent of San Silvestro in Capite (she also lived for a period in St. Vincent's family home).
Vincent's relationship with San Silvestro became frequent in the 1830s when Sr. Mary Gertrude Vicentini asked him to be her spiritual director; she later gave the following testimony during the Process for his Beatification: "I came to know Vincent Pallotti at San Silvestro in Capite, where I often invited him to celebrate Mass; many times I made my confession to him and I often conferred with him on spiritual matters. The other nuns used to take advantage of his presence in order to hear his holy words".
On February 6th, 1838, he visited San Silvestro to enlist the help of the community in promoting the aim of the Pallottine Family, the Union of Catholic Apostolate, to revive faith and rekindle charity and spread these throughout the world, aggregating the community to the Pallottine Family and extending a Diploma to 'The Venerable Monastery of San Silvestro in Capite' as a record of this fact, a replica of which is still conserved in the rectory of San Silvestro today. Mother Mary Veronica of the Cross, another nun of the convent of whom Vincent became spiritual director records this visit as follows: "I became acquainted with Vincent Pallotti when he came to San Silvestro in order to inscribe the nuns in the Union of Catholic Apostolate; he preached a beautiful sermon in which he exhorted us to cooperate in the propagation of the faith throughout the world."
In 1839, the great Roman celebration of faith, the Octave of the Epiphany (instituted by Vincent Pallotti in 1836), was held at San Silvestro: Mass was celebrated in the various Eastern and Western rites with sermons given in the principal languages of Europe, concluding each day with Benediction led by a Cardinal assisted in their turn by the various ecclesiastical colleges of Rome. Mother Mary Veronica noted that St. Vincent had to overcome some strong initial reluctance on the part of the Mother Abbess and some nuns to allow the celebration to take place in San Silvestro: "He sought permission to hold the Octave in our church. The Mother Abbess and some of the other nuns were much opposed and even gave him some sharp answers, but Vincent, without betraying chagrin or disappointment, withdrew to the cortile to pray and then returning to the nuns, overcame all difficulties". She also left the following account: "The Octave was a great success and the nuns asked that it should be held here again. The Mother Abbess presented a silver crown to the image of the infant Jesus used in the functions ... During the course of the Octave I observed that Vincent was in the church almost continuously, reading from the pulpit before the sermons, praying, hearing confessions and directing the functions ... ". The confessionals used by St. Vincent are those now in use in the church. In order to be constantly present during the Octave, Vincent stayed in the clergy house of San Silvestro during those days, a fact attested to by his earliest biographer, Fr. Rafael Melia SAC, in recounting the following incident which took place during this Octave: 'Cardinal [Francesco] Tiberi had been struck with apoplexy [probably meaning a stroke) during three days, and having lost his senses had not been able to go to confession. Vincent being called, said the Litany of the Blessed Virgin Mary, blessed him and left him an image of the venerable canon Gaspar del Bufalo. Having returned to the church of San Silvestro, where during those days he resided on account of the Octave of the Epiphany, he spent the whole night in prayer. During that same night the Cardinal returned to his senses, asked to make his confession, received from the parish priest the Viaticum ... On the morrow an ecclesiastic went to Vincent to announce the favour received, which had filled all with wonder and invited him to pay a visit to the Cardinal. But Vincent through his humility declined the invitation ... ". A visit to the elderly Cardinal Giovanni de Gregorio during these days had a similar effect.
Vincent's interest in the San Silvestro nuns continued until his death. During the Roman Revolution of 1849, when the community was forced to leave the monastery and take refuge at Santa Pudenziana, he wrote them a beautiful letter full of consoling reflections and, paid them several visits in their temporary home. The nuns returned to San Silvestro after the failure of the Revolution.
Vincent died on January 22nd, 1850, but was remembered with great esteem by the sisters. In 1884, the Mother Abbess of the community, which by then had transferred to the monastery buildings of St. Cecilia, addressed a letter to the Holy See, praying for the speedy introduction of his Cause of Beatification: 'His virtues and the reputation of his sanctity are known in Rome as well as in many other places. The religious of this Monastery, when they recall him to mind, feel urged to love and serve God with ever greater fervour. Some of the sisters still remember him and his modest, devout and edifying appearance, as well as his holy counsels and the charity with which he ascribed this monastery, on February 6th, 1838, amongst the auxiliaries of the Union of Catholic Apostolate. They recollect as well the interest he took in the community at the time of the tribulations of 1849, and the letter which he wrote to comfort us on that occasion ... ".
In 1885 the church was entrusted to the pastoral care of the community of Priests and Brothers founded by St. Vincent, the Society of the Catholic Apostolate, and in this way his connection to San Silvestro continues up to the present day.