Abstract: Methyl formate is an important downstream product in coal chemical industry，which is mainly produced employing copper catalyst for methanol dehydrogenation. However，the agglomeration and sintering of copper are the key factors limiting the catalyst performance. A series of ordered hierarchical porous silica (HPS) presenting both mesopores and micropores were fabricated at different hydrothermal temperatures and used for preparing supported copper catalysts with ammonia evaporation and impregnation methods. Dehydrogenation of methanol to methyl formate (MF) over Cu/HPS catalysts was investigated and found that the catalyst activity decreased in the order of Cu/HPS-130> Cu/HPS-160> Cu/HPS-100> Cu/HPS-130-W. The characterization results show that the texture properties of HPS is heavily affected by the hydrothermal temperatures. The HPS-130 support shows more ordered hierarchical structure with appropriate pore size distribution compared with HPS-100 and HPS-160, which can promote the dispersion of Cu particles and prevent agglomeration and sintering of active copper species during the reaction. Moreover, the Cu/HPS-130 catalyst by the ammonia evaporation method exhibites the optimal catalytic performance with methanol conversion of 38.7% and MF selectivity of 79.8% under 0.2 MPa with 300 ℃, significantly superior to Cu/HPS-130-W prepared through impregnation method. The excellent catalytic performance of Cu/HPS-130 can be attributed to the formation of Cu-O-Si species, derived from the strong interaction between surface silica and copper precursor in the process of ammonia evaporation approach, which greatly inhibiteds the stripping of copper particles on the Cu/HPS catalysts.