Methyl　glycolate　has　broad　potential　applications　in　fine　chemical　fields　such　as　pharmaceuticals,　cosmetics,　coatings,　and　serves　as　an　important　intermediate　in　organic　synthesis.　A　series　of　hexagonal　boron　nitride　supported　Ag　catalysts　for　hydrogenation　of　dimethyl　oxalate　(DMO)　to　methyl　glycolate　(MG)　were　elaborately　investigated.　Ag　was　loaded　onto　oxygen-rich　hexagonal　boron　nitride　(Oh-BN)　and　commercial　hexagonal　boron　nitride　(Mh-BN)　to　prepare　the　Ag/Oh-BN　and　Ag/Mh-BN　catalysts　by　ammonia　evaporation　method.　Under　the　conditions　of　a　temperature　of　200　degrees　C,　a　hydrogen-to-ester　molar　ratio　of　100,　and　a　weight　hourly　weight　space　velocity　of　0.6　h(-)(1),　the　yield　of　MG　for　the　Ag/Oh-BN　catalyst　was　94.6%,　while　that　for　the　Ag/Mh-BN　catalyst　was　only　41.6%.　The　catalysts　were　comprehensively　analyzed　using　a　variety　of　characterization　techniques　such　as　BET,　ICP,　XRD,　XPS,　TEM,　FTIR,　H2-TPR,　and　NH3-TPD.　The　results　showed　that　the　Ag/Oh-BN　catalyst　exhibits　smaller　particle　sizes　and　higher　binding　energy　compared　to　the　Ag/Mh-BN　catalyst.　The　higher　binding　energy　of　Ag　in　Ag/Oh-BN　arised　from　the　hybridization　between　p　orbitals　of　O　atom　in　B2O3　and　d-orbitals　of　Ag　atom,　leading　to　partial　electron　transfer　from　Ag　to　B2O3.　In　addition,　incorporating　a　controlled　amount　of　B2O3　into　commercial　hexagonal　boron　nitride　(Mh-BN)　produced　the　Ag/Mh-BN|xB(2)O(3)　catalyst.　The　Ag　particle　size　and　electronic　environment　in　this　catalyst　closely　resembled　those　of　the　Ag/Oh-BN　catalyst,　providing　further　evidence　of　the　critical　role　of　B2O3.