Instituted on 24 November 1714 by Peter the Great on the occasion of his marriage to Catherine I of Russia.

For the majority of the time of Imperial Russia, it was the only award for women; the Insignia of Saint Olga existed briefly from 1916 to 1917, but ceased with the fall of the Romanov dynasty.

The award was bestowed in two classes: Every Russian Grand Duchess was conferred the Grand Cross of the Order at her christening (or marriage into the Romanov family), and Princesses of the Imperial Blood were invested upon attaining their majority at 18.

The Dames Small Cross were all women of the highest nobility, who were part of the suite of the Empress and had engaged in important philanthropic or charitable works outside of their duties at Court.

The Hall of Saint Catherine in the Great Kremlin Palace in Moscow was used for these occasions.