The Palace was built for the Provana di Druent family, one of the many branches of the ancient and noble family. Ottavio Provana called upon several artists of the time to embellish the rooms of the palace, imprinting his particular personal taste. In particular, he commissioned the completion of the grand entrance hall to the architect Baroncelli, who had already executed the conclusion of Guarino Guarini's project at Palazzo Carignano.

At the end of the 17th century, thanks to the marriage between Elena Matilde di Provana and Gerolamo Falletti, the Palace passed to the Marquises of Barolo, who entrusted the architect Benedetto Alfieri with the renovation of some rooms on the first floor. The last owners were Tancredi and his wife Juliette Colbert de Maulévrier, known to all simply as Giulia, married in Paris in 1806.

Giulia and Tancredi transformed the Palace into the most famous drawing room in Turin during the Risorgimento, but also an authentic center of Christian charity. In those same years, the Marquises, bound by a deep sense of friendship, hosted Silvio Pellico in their apartments as a librarian and secretary. Upon Giulia's death in 1864, the Palace passed to the Opera Pia Barolo, created by her in her will, which still owns it to this day.