He began an enduring relationship with architect Carlo Rossi in the late 1810s, producing works for the Yelagin and Mikhailovsky Palaces, and the General Staff Building.

Towards the end of his life Pimenov continued to carry out large commissions, his works adorned the Alexandrinsky Theatre and the Imperial Public Library.

[2] Pimenov's academic credentials gave him the right to travel and live abroad, though with the international upheaval of the Napoleonic Wars he elected not to do so, eventually spending his whole life in Russia.

[4] Pimenov depicted Prince Vladimir as a militant and courageous leader, trampling on a pagan altar with a sword in one hand and a wooden cross in the other.

[2] With the successful completion of this commission, Pimenov was given the task of creating a statue of Alexander Nevsky for the cathedral, which had originally been entrusted to Feodosiy Shchedrin [ru].

Pimenov completed this statue in 1811, depicting Alexander Nevsky after his victory, lowering his shield, removing his armor and turning to the sky.

[2][4] He held his post at the Academy alongside a position with the Imperial Porcelain Factory, which he joined on 15 June 1809, creating designs for vases, dishes and statuettes.

[4][5] Among his later works for the factory were "The transition of Russian troops across the Danube" and "The patronage of Russia of Moldova and Wallachia", created in 1829 in response to the Russo-Turkish War.

[2] In 1815 he worked on the decorations for Andreyan Zakharov's Admiralty building, creating sixteen statues to serve as allegorical representations of elements and seasons - "Fire", "Summer", "Air", continents - "Asia", "America", and rivers - "Dnepr", "Neva".

[4][5] In the Yelagin Palace Pimenov created statues for the facades of the kitchen building: bas-reliefs for the greenhouse and high-relief figures for the lobby.

[4] For the Mikhailovsky Palace his work included the composition of winged figures of Glory, trophies in the timpanas of the main facade and numerous reliefs above the ground floor windows.

[2] Pimenov's later work included the chariot of Apollo for the Alexandrinsky Theatre between 1831 and 1832, and statues of Homer and Plato for the Imperial Public Library over the same period.