From the view point of green chemistry, CO2 utilization technologies with solar energy including the photoredox system have been received a lot of attention. As one of them, photoredox system containing a photosensitizer and a catalyst catalyzing a reaction of a carbon–carbon bond formation from CO2 as a feed stock were constructed. In a recent study, we reported the visible light-induced malate (C4 compound) production from pyruvate (C3 compound) and CO2 due to carbon–carbon bond formation with the system consisting an electron donor, a photosensitizer, diphenylviologen (PV2+) derivative as an electron mediator in the presence of malic enzyme (ME). However, the interaction between a photosensitizer and PV2+ derivative has not been clarified yet. In this study, water-soluble PV2+ derivative, 1,1′-bis(p-sulfonatophenyl)-4,4′-bipyridinium salt (PSV2+) was synthesized, and its electro-, photochemical properties were evaluated. Moreover, the photoredox properties of PSV2+ with water-soluble Zn porphyrin were studied using fluorescence spectroscopy and steady state irradiation. The fluorescence of Zn porphyrin was quenched by PSV2+ and the two-electron reduced form of PSV2+ were produced with Zn porphyrin with steady state irradiation. In addition, reaction solution containing triethanolamine, tetraphenylporphyrin tetrasulfonate, pyruvate, ME, Mg2+ and PSV2+ in CO2 saturated bis-tris buffer (pH 7.4) was irradiated with visible light, the oxaloacetate and malate were produced. This result indicates that PSV2+ is an efficient electron mediator in the visible light-induced redox system for carbon–carbon bond formation with ME from CO2 as a feedstock.