The photophysical and photochemical properties of the tetra- and octa-12-crown-4-substituted zinc (II) phthalocyanines are reported for the first time in the scope of this work. The new compounds have been characterized by elemental analysis, IR, (1)H and (13)C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields. and fluorescence lifetimes of these compounds in dimethylsulphoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for photodynamic therapy (PDT) applications. The effects of the substituents on the photophysical and photochemical parameters of the zinc (II) phthalocyanines (5, 6 and 7) are also reported. The singlet oxygen quantum yields (phi(Delta)) ranged from 0.48 to 0.78 are indicating the potential of the complexes as photosensitizers in applications of PDT. The fluorescences of the substituted ZnPc complexes are effectively quenched by benzoquinone (BQ) (C) 2009 Elsevier B.V. All rights reserved.