Ordered mesoporous carbons (OMCs) were used as supports to prepare Wacker-type catalysts for diethyl carbonate (DEC) synthesis by oxidative carbonylation of ethanol in a gas-phase reaction. The effect of support structure on the dispersion of the active species and catalytic properties were investigated. Nitrogen sorption, X-ray diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the active components have encapsulated in pore channels of OMCs. Characterizations of the catalysts, such as TEM, scanning electron microscope (SEM) and XRD, indicated that active components supported on OMCs have better dispersion compared to activated carbon (AC). The ethanol conversion of the catalysts was improved by approximate to 65% using OMCs as the catalyst support than AC. The stability of the catalytic activity can also be enhanced through surface modification of OMCs. Surface oxygen-containing groups (OCGs) on OMCs before and after surface modification were characterized by transmission IR spectra and the Beohm titration. The relationship between surface OCGs and anchor ability of OMCs was studied. (c) 2013 American Institute of Chemical Engineers AIChE J, 59: 3797-3805, 2013