Abstract Herein, we report the synthesis of a double hydrazone capable of undergoing photochemical E / Z isomerization through the imine double bonds. The bis(hydrazone) 1‐ E , E can be considered as a “two‐arm” system in which the controlled movement of each arm is obtained by photo‐modulation, making possible the appearance of two isolable metastable isomeric states 1‐ E , Z and 1‐ Z , Z . Such states are characterized by very specific structural, optical, and electrochemical properties. The latter allows the reversible return from either 1‐ E , Z or 1‐ Z , Z to the 1‐ E , E state. Our results are of great importance in the further development of molecular machines and photochemically controlled reactions by introducing for the first time double hydrazones as tunable photochemical switches.