Through a natural tree grain template and sol-gel technology, the heterogeneous catalytic materials based on polyoxometalate compounds H3[PM12O40] encapsulating SiO2: SiO2@H3[PM12O40] (SiO2@PM12, M = W, Mo) with core-shell structure had been prepared. The structure and morphology of the core-shell microspheres were characterized by the XRD, IR spectroscopy, UV-Vis absorbance, and SEM. These microsphere materials can be used as heterogeneous catalysts with high activity and stability for catalytic wet air oxidation of pollutant dyes safranine T (ST) at room condition. The results show that the catalysts have excellent catalytic activity in treatment of wastewater containing 10 mg/L ST, and 94% of color can be removed within 60 min. Under different cycling runs, it is shown that the catalysts are stable under such operating conditions and the leaching tests show negligible leaching effect owing to the lesser dissolution.