2(3),9(10),16(17),23(24)-tri-(4-phenylimine phenoxy) phthalocyanine zinc(Ⅱ) (C84H52N12O4Zn)(APc) and 2(3)-(2-methyl-8-quinolinoxy)-9(10),16(17),23(24)-tetra- (4-phenylimine phenoxy phthalocyanine zinc(Ⅱ) (C81H50N12O4Zn) (BPc) were synthesized from 4-hydroxybenzaldehyde and characterized by UV-Vis, IR, 1H NMR spectra and elemental analysis. The aggregative behavior was studied in DMF by UV-Vis. The results show that BPc is not aggregative in DMF. However, APc is aggregative in DMF at the concentration of 1.499×10-5 mol/L～2.407×10-5 mol/L. The Q-band maximum absorption peaks of APc and BPc at 672nm and 676nm, compared with the unsubstituted zinc phthalocyanine(669nm) have red shift obviously. The electrochemical properties and energy band structure are studied by cyclic voltammetry. They have low LUMO (－5.411 eV，－5.384 eV) and a deep HOMO (－4.214 eV，－4.210 eV) energy level. It is indicated that APc and BPc matches with the energy level of the nanocrystalline of TiO2.