For the first time in history, investigations of old Russian wall painting discovered green copper pigments. The first three malachite, atacamite, and poznyakite are artificial in origin, the fourth one is natural pseudomalachite. Poznyakite, hydrated copper sulfate, was identified for the first time in the history of investigating wall and easel painting. The synthesis of malachite, atacamite, and poznyakite was carried out. The form and structure of the synthesized compounds and the pigments from a paint coating completely coincide.