Detailed electrochemical studies have been carried out in basic, neutral buffer and neutral electrolyte medium. Both Co3O4 and Co3-xNixO4 were found active for oxygen evolution reaction (OER) with an interesting behavior in doped compound. It is found that lower nickel doping significantly enhances the OER activity in all the mediums; basic, neutral and neutral buffer. Figure 1 depicts that just 0.5% Ni-doped Co3O4 (Co2.985Ni0.015O4) is far more active than Co3O4 both in terms of current density and onset potential in K2SO4 medium. This enhancement nevertheless decreases once the doping concentration reaches beyond 0.5%. Figure 2 shows that OER activity (chronoamperomertic current) of Co3O4 increases after 0.25% Ni doping peaking at 0.5% and thereafter the reduction in the activity takes place. 1% Ni doped Co3O4 is less active than 0.25% Ni doped Co3O4. Once the doping concentration is 2.5% there is no enhancement in the activity compared to Co3O4. In the same way no effect is seen at 5 and 10% doping of Ni and the activity is similar to parent Co3O4. Same trend is observed in all other medium. Interestingly, in phosphate buffer solution (PBS) Co3O4 and 0.5% Ni-doped Co3O4 show OER at near thermodynamic potential i.e at a very low over potential. Similar effect was observed by Nocera and co-workers on cobalt oxide 1-2. This conclusively states that Co3O4 and its doped variant form similar type of in situ active sites as noticed Nocera and co-workers.