Cyclometalated Ru(II) complexes having a 3-phenylbenzo[b][1,6]naphthyridine (phbn) ligand have been synthesized and characterized by spectroscopic methods. The photo- and electrochemical redox behavior of the complexes are demonstrated. Complex [Ru(phbn)(bpy)(2)]PF6 ([1]PF6) readily undergoes proton coupled two electron reduction by chemical, electrochemical, and photochemical methods to generate [Ru(phbnHH)(bpy)(2)]PF6 ([1HH]PF6). The photochemical oxidation of [1HH]PF6 was also observed in presence of p-chloranil.