In this study, we investigated the overpotential of precipitation related to the catalytic activity of electrodes on the initial process of electrodeposition of Co and Co-Ni alloys on polycrystalline Cu substrates. In the case of Co electrodeposition, the surface morphology and the magnetic property change depending on the film thickness, and the relationship with the electrode potential fluctuation was shown. Initially, the deposition potential(−170 mV) of the Cu electrode as a substrate was shown, the electrode potential(Edep) at the Ton of electrodeposition and the deposition potential(−600 mV) of the surface of the electrodeposited Co film after Toff and when the pulse current was completed were shown. No significant change in the electrode potential value was observed when the pulse current was energized. However, in a range of number of pulses up to 5, there was a small fluctuation in the values of Edep and Eimm. In addition, in the Co-Ni alloy electrodeposition, the deposition potential(−280 mV) of the Cu electrode as the substrate exhibited the deposition potential(−615 mV) of the electrodeposited Co-Ni alloy after pulsed current application, the Edep of electrodeposition at the Ton of each pulse and the Eimm at the Toff varied greatly each time the pulse current was applied. From 20 % to less than 90% of the Co content of the thin film was continuously changed, and the value was constant at a pulse number of 100 or more. In any case, it was found that the shape of the substrate had a great influence.