Photocatalytic　trifluoromethylation　has　been　considered　as　an　efficient　method　to　introduce　trifluoromethyl　groups　into　organic　substances.　However,　the　relatively　high　cost　and　toxic　feature　of　the　metal-based　photocatalysts　have　become　major　obstacles　for　their　further　applications　in　this　area.　In　this　work,　graphene　oxide　sheets　have　been　successfully　utilized　as　a　kind　of　metal-free　photocatalyst　for　the　trifluoromethylation　of　arenes,　using　inexpensive　CF3SO2Na　as　the　CF3　radical　source.　It　is　shown　that　graphene　oxide　sheets　exhibit　suitable　bandgaps　under　visible　light　irradiation　to　photocatalyse　the　oxide　CF3SO2Na　to　form　the　electrophilic　radical　CF3,　which　efficiently　induces　the　trifluoromethylation　of　typical　benzene　molecules　and　some　of　their　derivatives.　©　2019　The　Royal　Society　of　Chemistry　and　the　Centre　National　de　la　Recherche　Scientifique.