alpha-Substituted unsymmetrical phthalocyanines fused with one through three TTF units were prepared from mixed 3,6-dioctyloxyphthalonitrile and 3,6-dioctylphthalonitrile bearing a TTF unit. The optical and electrochemical properties of the products were determined by UV-vis spectroscopy and cyclic voltammetry. Mono-TTF-annulated phthalocyanine and iodine produced the electron transfer complex which showed the radical cationic character.