In this work, voltammetric, spectroelectrochemical, and electrocatalytic properties of the metallophthalocyanines bearing four chloro and four biphenyl-malonic ester bulky groups were investigated. Voltammetric and spectroelectrochemical measurements of the metallophthalocyanines show that while cobalt phthalocyanine presents both metal-based and ring-based redox processes, all other complexes give only ring-based reduction and oxidation processes. The redox processes have generally diffusion-controlled, reversible and one-electron transferred mechanisms. Cobalt phthalocyanine electrocoated easily on the glassy carbon working electrode during the repeating cycles, a very useful feature for application in fabrication of thin films. Electrocatalytic activity of cobalt phthalocyanine to hydrogen evolution reaction was studied in solution titrated with perchloric acid and on glassy carbon electrode modified with cobalt phthalocyanine in aqueous solution. Electrocatalytic measurements show that cobalt phthalocyanine has significant catalytic activities towards hydrogen evolution reaction. Moreover, the catalytic activity of the complex enhanced significantly when the complex was incorporated into the cation exchange Nafion polymeric matrix.