So far as we know, metal-free phthalocyanine (PcH2) derivatives have never been synthesized by microwave heating. Recently, we have succeeded in synthesis of the metal-free derivative ((C8S)8PcH2: 3) in high yield (71%) for 10 min irradiation of microwave, by using glycerin as the reaction solvent. Furthermore, the corresponding copper (II) complex ((C8S)8PcH2: 4) could be also synthesized in 64% yield for 10 min. In comparison with the conventional solvent-free syntheses, it was much easier to separate and purify these Pc derivatives from the resulted crude products.