This study investigated the simultaneous in situ formation of Ni-based catalysts at the anode and cathode for glycerol oxidation and hydrogen evolution, respectively. The formation of electrocatalysts and their immobilization on the electrode surface occur simultaneously, avoiding the tedious and laborious procedures for the preparation and immobilization of the electrocatalysts. Ni salt in the homogeneous solution was deposited to repair the Ni-based electrocatalysts on the electrode surface, accompanied by the electrolysis of glycerol at the anode and the hydrogen evolution reaction at the cathode, exhibiting good working stability. This technique may find potential applications in the conversion of solar energy into storable fuels via the electrolysis of H2O or small molecules to produce hydrogen.