A　series　of　Fe-modified　CeO2　catalysts　with　nanoparticle,　nanorod,　nanocube　and　nano-octahedron　morphologies　were　synthesized　and　applied　for　direct　synthesis　of　dimethyl　carbonate　(DMC)　from　CO2　and　methanol.　The　Fe-modification　shows　a　remarkably　promoting　effect　on　the　formation　of　DMC　over　Fe-modified　CeO2　nanorod.　The　DMC　yield　was　improved　from　0.202　to　2.568　mmol　DMC　per　g(cat)　by　2　%Fe-modification　of　CeO2　nanorod.　A　synergistic　effect　among　the　moderate　acid-basic　sites,　specific　surface　area　and　surface　composition　resulted　from　Fe-modification　was　proposed　to　be　crucial　to　obtaining　the　high　reactivity　of　DMC　formation.