Highly active and selective Cu/SiO2 catalysts for hydrogenation of dimethyl oxalate(DMO) to ethylene glycol(EG) were successfully prepared by means of a convenient one-pot synthetic method with tetraethoxysi lane(TEOS) as the source of silica. XRD, H2-TPR, SEM, TEM, XRF and N2 physisorption measurements were performed to characterize the texture and structure of Cu/SiO2 catalysts with different copper loadings. The active components were highly dispersed on SiO2 supports. Furthermore, the coexistence of Cu0 and Cu+ contributed a lot to the excellent performance of Cu-TEOS catalysts. The DMO conversion reached 100% and the EG selectivity reached 95% at 498 K and 2 MPa with a high liquid hourly space velocity over the 27-Cu-TEOS catalyst with an actual cop per loading of 19.0%(mass fraction).