The effect due to systematic substitution of cobalt by iron in La_0.6Ca_0.4Co_1-xFe_xO₃ towards the oxygen evolution reaction (OER) in alkaline media has been investigated. These compounds were synthesized by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order towards OH^- near unity were achieved for the unsubstituted La_0.6Ca_0.4CoO₃. A decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La_0.6Ca_0.4Co_0.2Fe_0.8O₃ and La_0.6Ca_0.4Co_0.1Fe_0.9O₃ showed higher area specific activity towards OER than La_0.6Ca_0.4CoO₃ or La_0.6Ca_0.4FeO_3. We believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.