The influence of some transition metal ion substitutions in the active 0.2 mole strontium-doped lanthanum cobaltate (La0.8Sr0.2Co1-yByO3 with B = Ni, Fe, Cu, and Cr; 0.1 less than or equal to y less than or equal to 0.4) lattice was studied on the electrocatalytic properties of the oxide by cyclic voltammetry and Tafel polarization techniques. The cyclic voltammetry showed a pair of redox peaks prior to the onset of oxygen evolution; regardless of the nature of the substitution. The presence of Fe or Ni, in small quantities, enhanced the electrochemically active area. The anodic polarization studies indicated two Tafel slopes : similar to 2.3 RT/F at low and similar to 2(2.3 RT/F) at high overpotentials. The oxygen evolution reaction on each B-site substituted perovskite followed first-order kinetics with respect to OH- ion concentration. The La0.8Sr0.2Co0.9Fe0.1O3 and La0.8Sr0.2Co0.9Ni0.1O3 electrodes showed the highest electrocatalytic activity based on geometrical surface area. Copper and chromium substitutions had detrimental effects on the electrocatalytic activity.