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[Display omitted] • Co-Ag x /TiO 2 catalyst with low metal content were synthesized. • Co-Ag 0.7 /TiO 2 catalyst exhibits exceptional hydrogenation performance of dimethyl oxalate. • The catalyst achieves excellent catalytic performance at lower hydrogen consumption. • The synergistic interaction between Co and Ag is conducive to the adsorption and activation of DMO and H 2. • Providing a potential new avenue for designing low loading catalysts for dimethyl oxalate hydrogenation. The Co-Ag x /TiO 2 catalysts with low mass content of Co and Ag were synthesized through the impregnation method and investigated for dimethyl oxalate (DMO) hydrogenation to methyl glycolate (MG). Remarkably, the Co-Ag 0.7 /TiO 2 catalyst with an Ag concentration of 0.7 wt%, exhibited an impressive yield of MG of ∼94.4 %, surpassing the yields of MG obtained with Co/TiO 2 (∼54 %) and Ag 0.7 /TiO 2 (∼69 %) catalysts. Various characterizations elucidated that the exceptional catalytic performance of Co-Ag 0.7 /TiO 2 can be ascribed to the synergy between Co and Ag, resulting in the formation of AgCoO 2 as high active site can improve the adsorption and activation of DMO and H 2 on catalyst surface. Additionally, the doping of a small amount of Ag regulated the contents of Lewis acidic and Brønsted acidic sites, leading to a high conversion of DMO and selectivity of MG. Furthermore, the excellent MG yield and long-term stability (at least 200 h) facilely obtained over our catalyst under mild reaction conditions guarantee a feasible prospect in the industrial application. This study not only unraveled the superior performance of the Co-Ag synergistic catalyst, but also carried significant implications for developing catalysts with low-content in DMO hydrogenation to MG. [ABSTRACT FROM AUTHOR]