Developing efficient catalysts for the selective hydrogenation of dimethyl oxalate (DMO) is of great significance for the coal-based production of methyl glycolate (MG), but designing processes for this conversion is challenging. Herein we report an unprecedented catalytic performance for the selective hydrogenation of DMO to MG, achieved by using a catalyst based on Ag nanoparticles anchored inside the mesopores of amine-derivatized silica nanospheres (NH2-MSNS). It was determined that the unique microenvironment endowed by the amine-derivatized channel surfaces helps this Ag catalyst promote the activation of DMO and H-2 to yield MG with high selectivity, and also prevents sintering and coking, hence improving stability. Accordingly, the resulting Ag/NH2-MSNS catalyst was shown to be capable of promoting the hydrogenation reaction with a turnover frequency of 230 h(-1) and a MG selectivity of 97% at nearly 100% of DMO conversion, a performance that was sustained for at least 250 h; these results are significantly better than those seen with other reported catalysts. Our study points to a promising route for the development of high-performing Ag catalysts to be used in the coal-based MG production. (C) 2020 Elsevier Inc. All rights reserved.