A heterogeneous bifunctional hybrid catalyst originated from copper tetrasulfophthalocyanine (CuPcTs) and hydrotalcite for Baeyer-Villiger (B-V) oxidation has been prepared and characterized. XRD, FTIR, DR UV-Vis and SEM characterization indicate that CuPcTs molecule has been successfully intercalated into the layer of ZnAl hydrotalcite. And the synthesized hybrid exhibited excellent catalytic activity in the B-V oxidation for various ketones under mild conditions. Its bifunctional role in the reaction through O-2/benzaldehyde has been discussed and verified by controlled experiments. The study indicates that the designed catalyst not only catalyzes the oxidation of benzaldehyde to perbenzoic acid, but also accelerates the transformation of ketone to lactone or ester. [GRAPHICS] .