Molecular hybrid materials formed from polyoxometalates dispersed in conducting polymers represent an innovative concept in energy storage. This work reports in detail the first practical realization of electrodes based on these materials for energy storage in electrochemical supercapacitors. The molecular hybrids PAni/H4SiW12O40, PAni/H3PW12O40, and PAni/H3PMO12O40 (PAni: polyaniline) have been prepared electrochemically on platinum or carbon substrates, with PAni/H3PMO12O40 being the prototypical example presenting the best energy-storage performance in the series. This hybrid displays the combined activity of its organic and inorganic components to store and release charge in solid-state electrochemical capacitor cells, leading to a promising value of 120 Fg(-1) and good cyclability beyond 1000 cycles.