4-(2′,3′,4′,5′,6′-Pentafluorobenzyloxy)phthalonitrile was employed with hexanethiol to prepare 4-(2′,3′,5′,6′-tetrafluoro-4′-hexylthio-benzyloxy)phthalonitrile, by the selective displacement of the para-fluorine atom using K 2 CO 3 in DMF. The new Zn(II), Ni(II) and Co(II) phthalocyanines with four, peripheral fluoro-hexylthiobenzyloxy groups were synthesized from 4-(2′,3′,5′,6′-tetrafluoro-4′-hexylthio-benzyloxy)phthalonitrile and the corresponding divalent metal salt (Zn(CH 3 COO) 2 , NiCl 2 or CoCl 2 ). The blue-green phthalocyanines were soluble in common organic solvents. The structures of the target compounds were confirmed using elemental analysis, UV–vis, FT-IR, 1 H NMR, 19 F NMR and mass spectroscopic methods.