The youngest son of Count Pavel Andreyevich Shuvalov and Princess Varvara Petrovna Shakhovskaya, the heiress of the Ural mining factories. On his father's side, he was the great-grandson of Field Marshal Count P. I. Shuvalov, and on his mother's side, a descendant of the miner A. G. Stroganov. He was born in Saint Petersburg on September 14, 1819, and was baptized on September 18 at St. Isaac's Cathedral, where his grandparents Shakhovskaya were his godparents.

Having lost his father early, he and his brother Andrey were raised by their mother. Their official guardian was the family friend M. M. Speransky, who personally oversaw their education and selected teachers. He spent most of his childhood and youth abroad.

He graduated from the law faculty of Saint Petersburg University and attended meetings of the "Circle of 16." In January 1837, together with Prince Vyazemsky, he visited Pushkin's apartment to bid farewell to the poet. He began his service in the court rank of chamber junker and from 1856 became an unofficial assistant secretary of the State Council. In 1857 and 1862, he was the governor of the nobility in Saint Petersburg. From 1860, he held the position of actual state councilor and chamberlain. From 1857 to 1863, he was a member of the Board of Trustees of public welfare institutions in Saint Petersburg. He headed the Petersburg Noble Committee for preparing the peasant reform of 1861. According to Prince P. V. Dolgorukov, Count Shuvalov was a kind and not unintelligent man, but weak and indecisive, incapable of decisive actions.

After retiring in 1863, he lived in resorts in France and Germany.

In 1864, V. P. Shakhovskaya signed a "preliminary domestic act," and on June 1, 1865, in Paris, a will. In the first document, she transferred the Perm ancestral estate to her sons in full ownership. On April 26, 1864, brothers Pyotr Pavlovich and Andrey Pavlovich divided it into two parts. Andrey Pavlovich received the Yugo-Kamsky factory and the Novo-Usolsky and Lenvensky salt mines with land plots totaling 440,400 desyatinas. Pyotr Pavlovich received the Lysvensky, Biserksy, and part of the Kusye-Alexandrovsky factory, as well as the Krestovozdvizhensky gold and platinum mines and 496,156 desyatinas of land. The princess retained only the redemption loans of former serfs. In 1884, he founded the Teplogorsky factory.

In his later years, he lived in the estate of the village of Talnoye, Kyiv province, where he died on July 14, 1900, and was buried near the Holy Trinity Church. According to A. A. Polovtsov, Count Shuvalov was a model of honesty and nobility, humanity, and politeness. He was a true nobleman, possessing a vast fortune and an interest in knowledge, such as history and numismatics, in which he was considered an expert. However, his scholarship was only a small part of his virtues.