Phthalocyanine catalysts were synthesized and supported matel phthalocyanines were found to be good catalysts for benzene hydroxylation to phenol. Matel phthalocyanines were characterized by N2 absorption-desorption, FT-IR spectroscopy, and tranmsission electron microscopy. The experimental results suggested that the supported matel phthalocyanines were good catalysts for benzene hydoxylation reaction. Supported vanadium phthalocyanine performed the best catalytic activity, on which 11.6% of phenol yield and 100% of selectivity were obtained. And it was proved to be reusable in this reaction.