This paper describes an emerging synthetic route for acetoin production via the anaerobic dehydrogenation of 2,3-butanediol to give a deep understanding of the specific dehydrogenation behavior of diols. Cu/SBA-15-x-T prepared by the ammonia evaporation method was applied to the dehydrogenation of 2,3-butanediol. The results of XRD, FTIR, H₂-TPR, XPS, and NH₃-TPD characterization verified that the CuO-like phase, with a Cu²⁺O²⁻ pair, existed in the form of -Si-O-Cu-O-Si- structures in Cu/SBA-15-x-T catalysts. The amounts of the CuO-like phase and Cu⁰ can be tuned simultaneously by adjusting the synthetic solution alkalinity and reduction temperature to achieve an optimal synergic effect between the CuO-like phase and Cu⁰ sites. Compared with the catalytic inertness of Cu catalysts prepared by the conventional impregnation method, the resulting Cu/SBA-15-10.0-300 showed superior catalytic performance (reaction rate: 9.90 × 10⁻³ mol·min⁻¹g⁻¹) in 2,3-butanediol dehydrogenation. Studies on the structure–performance correlation based on the kinetic study revealed that the catalytic activity of Cu/SBA-15-x-T catalysts is attributable to synergic catalysis between the interfacial CuO-like phase and Cu⁰ sites, which favors the bond cleavage of O-H and α-C-H, respectively.