The present invention relates to a process for cathodic protection of electrode or electrode materials wherein negative bias is applied on the electrode. the negative bias is obtained by asymmetric current pulse. The asymmetric current pulse is obtained by performing negative phase with higher amplitude. The asymmetric current pulse is obtained by performing negative phase with wider pulse width than that of the anodic phase. The asymmetric current pulse is obtained by performing negative phase with higher amplitude and with wider pulse width than that of the anodic phase. The present invention further relates to a process for cathodic protection of electrode or electrode materials, wherein negative bias is applied on the electrode, wherein the negative bias is obtained by asymmetric current pulse, wherein the asymmetric current pulse is obtained by performing negative phase with wider pulse width than that of the anodic phase. The wider pulse width is obtained by pulse trains.