This study focuses on the syntheses of zinc 5,10,15,20-tetrakis(p-tolyl) porphyrin (ZnTTP), silicon dichloride 5,10,15,20-tetrakis(p-tolyl) porphyrin (SiCl(2)TTP), and oxotitanium(IV) 5,10,15,20-tetrakis(p-tolyl) porphyrin (TiOTTP) and their photovoltaic properties as additives for use in electrolytes of the DSSC. In order to investigate photovoltaic effects of the DSSC devices, the FTO/TiO(2)/N3 Dye/Electrolyte/Pt device was fabricated by using poly (ethylene glycol) (PEG) electrolytes based on TTP metal complexes as an additive. When TiOTTP was introduced into the PEG electrolyte, the power conversion efficiency of DSSC device was shown remarkably a high value compared with values of the others.