A series of axial di-substituted silicon(IV) phthalocyanines with electron-donating and electron-withdrawing properties were synthesized. The compounds were characterized by elemental analysis, 1H NMR, IR, and ESI-MS. The effect of axialligands on the photophysical properties of siliconphthalocyanines was studied by UV/Vis, steady-state and time-resolved fluorescence spectroscopic analyses. Compared