Abstract: In the present paper studies were made on the syntheses and photoelectric effects of tetraphenylporphyrin complexes of elements Al(Ⅲ),Ga(Ⅲ)In(Ⅲ),Si(Ⅳ),Ge(Ⅳ),Sn(Ⅳ),Bi(Ⅲ).The results showed that the methods of syntheses of tetraphenylporphyrih complexes of Si(Ⅳ),Ge(Ⅳ),Bi(Ⅲ)were improved and the photoelectric effects of tetra-phenylporphyrin complexes of these elements were better than those of the tetraphenylphorphyrin complexes of the transition metals These good results were in accord with the stable electronic configurations(ns²np⁶ or nd¹⁰ )of the central metal ions.Ge(Ⅳ)tetraphenylporphyrin gave the best result(0.78Vand 1.6μA/cm²).The photovoltage of Ge(Ⅳ)was up to1.15(with reference to the standard hydrogen electrode).