A new water-soluble zinc phthalocyanine, 2,9,16,23-tetrakis[4-(1-naphthoxy-4-sulfonic acid sodium salt)] phthalocyaninato zinc NhtZnPc, where Nht indicates the naphthoxy-4-sulfonic acid sodium salt, was synthesized and its electrochemical and spectroelectrochemical properties were investigated in DMSO solution. The formation of NhtZnPc was monitored with the UV-vis spectral changes of NhtH(2)Pc in MeOH solution. The electrochemical studies showed that NhtZnPc displayed two reduction waves assigned to Pc(3-)/Pc(2-) and Pc(4-)/Pc(3-) couples, while it also showed one oxidation wave which was assigned to Pc(-)/Pc(2-) couples. The half-wave potential of the first reduction is shifted by 0.067 V compared to that of unsubstituted metal-free phthalocyanine (H2Pc). This result shows that the weak electron-withdrawing sulfonated-naphthoxy groups on macrocyle core make the reduction processes of NhtZnPc easier in DMSO solution. The spectroelectrochemical results showed that the first reduction product exhibited the characteristic spectral changes corresponding to mono-anionic species of zinc phthalocyanine having long-term stability during the reduction process. But, the second reduction product resulted in unstable di-anionic forms in DMSO.