According to the decree "On the Rules for Managing and Preserving in Order and Integrity the Treasures in the Workshop and Armoury Chamber" signed by Emperor Alexander I on the 10th of March 1806, the Workshop and the Armoury Chamber got the status of the museum. Peter Stepanovich Valuev, a Privy Councillor in deed, led the development of the concept, formation of the staff and the main activities for the creation of the museum. The decree completed the process of reforming the management system of the Kremlin treasury and became a turning point in the history of the creation of a museum in the Moscow Kremlin. It established rules and norms that allow us to say that from that time onwards the Workshop and Armoury Chamber began to develop as a museum institution with all its inherent functions.

According to the Rules, it was forbidden to sell or give away any valuables from the museum without a special order of the emperor. Responsibility for the preservation of items, their movement within the museum, the search for "treasures" previously issued from the chamber, as well as the responsibility for the staff of employees was entrusted to the head of the Workshop and the Armoury Chamber P.S. Valuev. The museum was under the jurisdiction of the Kremlin Buildings Maintenance and Repair Department, which was also headed by Valuev. However, due to the specificity of its activities the museum had its own special Bureau – staff of officials, office work, financing. The staff of the Chamber consisted of the Principal (D. I. Kiselev was appointed to this position), three indispensable members, the head of the office and his assistant, the secretary and the executor, heading 14 accountants, who performed technical work and observed the safety of the "chamber treasures ... during public viewing". The craftsmen, who had previously formed a significant part of the chamber's staff, were completely removed from it.

Special rescripts of the Emperor appointed honourable members of the Workshop and the Armoury Chamber. As a rule, these were well-known historians, culture figures and collectors who made an actual contribution to the study and acquisition of the museum's collections. Among them were N.I. Karamzin, A.I. Musin-Pushkin, A.N. Olenin, P.P. Svinyin and others.

In 1807, on the initiative of P.S. Valuev, the publication entitled "Historical Description of the Old Russian Museum, under the name of the Workshop and Armoury Chamber in Moscow" was released, in which the most important collections of the museum were published for the first time. It was compiled by A.F. Malinovsky, the first honorary member of the museum.

In 1806, the construction of the building for the museum was started according to the project of architect I.V. Egotov. Its construction and interior decoration continued until 1812. The work on creation of the first exposition in the museum was interrupted by the war.

A glorious page in the history of the museum was the rescue of the state treasury during the occupation of Moscow by Napoleon's troops. The staff of the Workshop and the Armoury Chamber managed to pack up the valuables and secretly transfer them to Nizhny Novgorod and then to Vladimir. In the summer of 1813 the items were safely returned to Moscow.

The first exposition of the museum was opened only in 1814, when it was headed by one of the most famous and influential nobles of his time, senator, member of the State Council, amateur and collector of antiquities Prince Nikolay Borisovich Yusupov.

Until August 1831 the organisational structure and staff of the museum remained practically unchanged. The chief attendants D.I. Kiselev, F.A. Ushakov, indispensable members of the chamber, clerks, executors, etc. carried out the daily work of accounting and storage of exhibits, organised public visits to the museum exposition.