The development of NO photoreleaser compounds has important potential applications on medicine, particularly on preventing topic infections and controlling cancers. Due to these expectations, the photochemical release of nitric oxide from complexes of [Ru(bpy)2LX]n+, where L = imidazole, 1-methylimidazole, sulphite and thiourea and X = NO+ and NO2− was investigated employing spectroscopic and electrochemical techniques. The release of NO was confirmed by chronoamperometry using a NO selective electrode, while the other product, mainly [RuIIH2O], was detected by UV-Visible spectroscopy and electrochemical techniques for all complexes except for thiourea. The amount of NO released by these complexes upon irradiation was determined using a new developed method using square wave voltammetry.