The development of new techniques for design and fabrication of efficient and durable electrocatalysts for water splitting into hydrogen and oxygen is a fundamental approach to one of the major challenges to meet future sustainable fuel demand. Herein, a novel polyoxometalate-based composite was formed onto rotating carbon paste electrode by two different immobilization techniques, including physical mixing method and direct formation method, and used as electrocatalysts for the oxygen evolution reaction (OER) in alkaline media. The comparisons of the electrochemical performance of these fabrication methods exhibited a high catalytic activity and stability toward OER for both immobilization techniques and gained a current density of 10 mA cm−2 at overpotential of 380 and 440 mV for direct formation and physical mixing methods, respectively.