The synthesis, characterization, and spectroscopic properties of novel nonperipherally tetrasubstituted metallophthalocyanines (zinc, cobalt, copper, manganese, and indium) bearing 4 (7-(trifluoromethyl)quinolin-4-yl)oxy units has been reported. The new compounds have been characterized using UV-Vis, IR, H-1 NMR, C-13 NMR, F-19 NMR, and mass spectroscopic data. The absorption properties of these new complexes were compared to those of peripherally substituted phthalocyanine derivatives. Based on the structural, spectroscopic, and absorption studies, it was found that the substitution effect altered the electronic structures significantly. The results provide useful information to understand the effect of peripheral or nonperipheral substitution on the properties of this macrocyclic ring. Photophysical properties with zinc(II) phthalocyanine were found, including electronic absorption and fluorescence quantum yield. The fluorescence of the complex was investigated in DMF and it was found that benzoquinone was an effective quencher.