The study of hydrogen and deuterium electrosorption into the palladium LVE (limited volume electrode) has been performed in acidic solutions. The hydrogen capacity, H(D)/Pd, measured electrochemically, depends significantly on sweep rate in cyclic voltammetric experiments and also on the thickness of the LVE. Two different mechanisms of hydrogen desorption, namely the electrochemical oxidation and the non-electrochemical recombination step, which take place in parallel within the Pd-LVE, have been postulated.