An experimental investigation of the electrochemical kinetics of the α‐palladium‐hydrogen system was made by means of a palladium bi‐electrode. The pH effect on the anodic and cathodic polarization behavior was determined and related to bi‐electrode mechanisms. Thickness of the bi‐electrode had no significant effect. It was found that catalytic activity for the hydrogen‐ producing reactions on α‐Pd was definitely less than that on β‐Pd. The fraction of the total current carried by proton flow in the bi‐electrode was determined.