Despite being explored extensively due to their excellent bifunctional performance, the role of the surface state of these bimetallic catalysts still needs to be explored due to their higher cation diversity. The doping of the secondary metal resulted in double spinel (a hybrid of both normal and inverted spinels), allowing us to improve the catalytic properties by creating more oxygen vacancies, which act as active sites and enhance thermal stability. Therefore, doping the secondary metal into Co3O4 is a judicious choice to obtain a catalyst with more active sites.