We use photosensitive resin as material, and adopt 3D printing and pyrolysis to prepare silica ceramics. HKUST-1 was grown on the ceramic surface by step-by-step in-situ growth method to obtain the HKUST-1/SiO2 composite material. The HKUST-1/SiO2 composite material was characterized by X-ray powder diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), thermogravimetric analysis (TG). The HKUST-1/SiO2 composite material not only has the characteristics of HKUST-1 and SiO2, but also can be designed into different complex shapes. In addition, the composite can be easy to separate from the product without centrifugation or filtration after the reaction is completed. The application of benzyl alcohol oxidation was an example to the performance of composite catalysts.