Utilizing urea homogeneous precipitation method, Cu and Mg species were successfully supported on SBA-15, KIT-6, and MCM-41 respectively for furfuryl alcohol (FFA) hydrogenolysis to 1,2-pentanediol (1,2-PeD). The catalytic results showed that the yield of 1,2-PeD followed the order of CuMg/SBA-15 > CuMg/KIT-6 > CuMg/MCM-41, especially the maximum of 50.0 % over CuMg/SBA-15 surpassing that of most copper-based catalysts reported. It is found that FFA conversion dramatically increases with the raising of Cu dispersion, attributing to the high exposure of active sites. Meanwhile, the selectivity of 1,2-PeD is strongly depended on the Cu0/Cu+ ratio of catalyst and CuMg/SBA-15 with the highest value of 57.6 % is derived from the largest Cu0/Cu+ ratio. In a word, CuMg/SBA-15 shows the excellent activity along with stability owing to the synergy between large Cu0/Cu+ ratio and good Cu dispersion, providing by two-dimensional hexagonal straight channel arrangement with generous pore diameter. Innovatively, it is put forward that dual adsorption sites of both MgO and Cu species in the CuMg/SBA-15 catalyst promote the FFA ring-opening to yield 1,2-PeD based on the comparison of Cu dispersion, metal-support (M−S) interaction and the adsorption capacity for furan rings with Cu/SBA-15. This study provides a novel approach for catalyst design for this reaction, focusing on optimizing the catalytic performance by fine-tuning structure of the support.