Nicholas I of Russia's daughter Grand Duchess Maria Nikolaïevna first had the idea of building a church for Florence's Russian community in 1873, but it was only six years later that a large gift from prince Paul Pavlovitch Demidoff of San Donato allowed construction to commence.
Pietro Berti was initially taken on to design it by archpriest Vladimir Levitsky, then curate of the Orthodox church at the Russian embassy.
Levitsky finally raised enough funds to build a permanent structure and in 1897 the Russian ambassador and foreign minister approved plans produced in 1890 by Preobrajensky.
Constantine I of Greece died in exile in Palermo on 11 January 1923 and later that year he was buried in the church, followed in 1926 by his mother queen Olga Constantinovna of Russia and in 1932 by his widow Sophia of Prussia.
All three sets of remains were moved to the Tatoi Palace in Greece in November 1936, a year after the restoration of the Greek monarchy.