Solid frustrated-Lewis-pair catalysts, based on Zn-Al composite oxide modified loaded with Au (Aux/ZnAl-CHT), were prepared by calcination of hydrotalcite precursors and tested for the direct synthesis of glycerol carbonate using CO2 as the carbon source. An Au5/ZnAl-CHT catalyst shows the highest catalytic performance with the glycerol carbonate yield of 19.5 % and the selectivity of 50.5 % at 170 °C and 4.0 MPa CO2, while maintaining good thermal stability and excellent regeneration ability. A series of characterization results and density functional theory (DFT) calculations indicated the introduction of Au leads to more frustrated-Lewis-pairs in Zn-Al composite oxide (ZnAl-CHT), which improve the adsorption and activation of CO2. Meanwhile, FTIR analysis indicates that glycerol is activated by Zn2+ for the formation of zinc glycerolate intermediates. The above dual synergistic activation processes effectively enhance the catalytic performance. And the reaction pathway is proposed for the synthesis of glycerol carbonate from CO2 and glycerol. Display omitted ●Au5/ZnAl-CHT exhibited excellent catalytic performance with the yield of 19.5 %.●Au played a potential “bridge” promoting the formation of FLPs.●Characterization results and DFT calculations indicated that Au led to more FLPs.●The reaction mechanism for direct synthesis of glycerol carbonate was proposed.