The dihydrogenated porphycene cobalt(ii) complex was synthesized and electrochemical experiments were carried out. The one-electron reduction of the complex proceeded at the central metal to afford the Co(i) species; in contrast, for the non-hydrogenated porphycene cobalt(ii) complex, the one-electron reduction gave the ligand reduced radical anion species. The reactivity of the one-electron reduced species with alkyl halides showed clear differences between the complexes. Hydrogenation of the β-position of the porphycene makes it possible to generate a central cobalt reduced species possessing a higher reactivity than the ligand reduced radical anion species.