Married life
Paul's troubled life was changed by his falling in love with a lady-in-waiting from Saint Petersburg, Princess Maria Mescherskaya. Paul met Maria in Paris in the spring of 1867.
His first marriage was 1 June 1867 to Princess Mariya Meshcherskaya (1844–1868). She died two days after giving birth to a son, Elim Pavlovich Demidov, 3rd Prince of San Donato, at Hietzing in the suburbs of Vienna 6 August 1868.
Losing his wife had a lasting effect on Paul, who remained inconsolable for a long time, spending a long while in the room in the Villa San Donato where Maria's dresses were kept, trying to recover her presence. Mother Aurora took charge of little Elim, who became very close to her grandmother. In October 1868, Paul and little Elim and Aurora moved to Paris, where they prepared a residence for themselves.
In the memory of his wife Paul set up a workplace for 200 women in the working-class district of Paris. The purpose of the department was to improve the moral and physical life situation of the working class. In 1869 he was appointed to the Kyiv Provincial Government. He held his office well and was promoted to mayor a year later.
Paul's uncle, Anatole Demidov, died in Florence in the spring of 1870. Paul permanently resigned from the civil service and moved on to live a great international life as Prince of San Donato. The mansion near San Donato in Florence with its valuable art collections was now been taken over by Paul Demidov.
He married secondly in Saint Petersburg 2 June 1871 to Princess Elena (Hélène) Petrovna Trubetskaya (1853–1917). The mother of the new spouse, Princess Elizabeth Trubetskaya, had lived most of her life in Paris, especially after the death of her husband Prince Pjotr Nikitich Trubetskoy (1826–1880).
They had six children:
Prince, Count Nikita Pavlovich Demidov (1872–1874)
Princess, Countess Aurora Pavlovna Demidova (1873–1904)
Anatoly Pavlovich Demidov, 4th Prince of San Donato (1874–1943)
Princess, Countess Maria Pavlovna Demidova (1877–1955)
Prince, Count Pavel Pavlovich Demidov (1879–1909)
Princess, Countess Elena Pavlovna Demidova (1884–1959)
Deciding that San Donato was too full of memories of his first wife, Paul bought in 1873 Pratolino, a large farm, from the estate of the Grand Duke of Tuscany. He immersed several millions in its restoration. When the castle-like Villa Pratolino, now known as Villa Demidoff, was ready to be inhabited, Paul and his family moved there from San Donato.
They ended up selling San Donato, and it was ceded on 5 November 1881 to Gaston Mestayer, a French business magnate, with the gardens sold separately to Nemesio Papucci and Rosselli Del Turco.
A significant portion of the Demidov collection, housed in 14 rooms at San Donato, was dispersed through a series of sales and public auctions. This included works from the “musée napoléonien” established on Elba by Anatoly Nikolaievich Demidov, 1st Prince of San Donato, as well as souvenirs that had largely been transferred to him by his father-in-law, Jérôme Bonaparte.