SBA-16 silica with intact surface hydroxyl groups were quickly obtained (5 min) via a fast-microwave-assisted method, and further adopted as an efficient template for the synthesis of three-dimensional (3D) ordered mesoporous CuO_x-CeO₂ catalysts (htpCCx) through a simple and reproducible host-guest interaction. The XRD, XPS, H₂-TPR, and Raman results reveal that plenty of Cu²⁺ ions in htpCCx are incorporated into CeO₂ lattice, leading to the formation of Cu_xCe_1-xO_2-δ solid solution, which produces large amounts of oxygen vacancies and enhances the metal reducibility. The interaction of Cu and Ce is essential to the reaction for maintaining the Cu²⁺/Cu¹⁺ and Ce⁴⁺/Ce³⁺ redox couples. Catalyst with 3D mesostructure possess remarkable enhanced low-temperature activity for epichlorohydrin combustion, and htpCC20 is indentified as the most powerful catalysts, e.g., the reaction rate at 165°C  over htpCC20 is about 6.3 and 33.3 times higher than that of the catalysts synthesized by the conventional incipient impregnation and thermal combustion methods, respectively. Furthermore, htpCC20 shows superior CO₂ selectivity (> 99%) and stability (no deactivation occurs after 50 h reaction). It is believed that the active phase dispersion, surface active oxygen density, and low-temperature reducibility are the dominant factors deciding the catalytic performance.