The anodic dissolution reaction of was found to proceed quantitatively in well‐stirred solutions of and with the formation of soluble, tripositive Ga and As compounds. Disintegration of the anode was noted under natural convection. Passivity ensued at high anodic currents in electrolyte, with an abrupt active‐passive transition and a gradual passive‐transpassive transition. In electrolyte, the passive region extended to the highest attainable anodic potentials. No substantial differences in electrochemical behavior were found between Ga(111) and surface orientations. The influence of the semiconductor properties of p‐type on the cathodic polarization was confined to low current densities. Galvanostatic anodic‐cathodic cycling revealed significant details of the photopotentials and eliminated the hysteresis in the cathodic polarization curves.