Covalently　functionalized　reduced　graphene　oxide　(RGO)　sheet　was　prepared　by　treating　nitrogen-centered　anions　generated　from　poly(9,9＇-diheylfluorene　carbazole)　(PCF)　with　GO.　The　resultant　hybrids　with　different　chemical　behavior　were　separated　by　centrifugation.　The　covalent　modification　was　fully　characterized　by　IR　spectroscopy,　UV/Vis　spectroscopy,　thermogravimetric　analysis　(TGA),　Raman　spectroscopy,　TEM,　and　SEM.　It　was　found　that　RGO-PCF-s,　the　soluble　part,　was　split　into　small　platelets　with　a　size　of　about　200　nm,　and　the　hydrophobic　polymer　PCF　became　hydrophilic　after　wrapping　by　RGO.　The　content　of　RGO　in　RGO-PCF-s　was　about　11.9　%,　and　the　hybrid　material　showed　good　dispersion　stability　in　water.　Besides,　RGO-PCF-i,　the　insoluble　part,　with　larger　size,　displayed　excellent　optical-limiting　response,　in　which　both　nonlinear　absorption　and　nonlinear　scattering　play　important　roles.　As　nitrogen-centered　anions　are　an　important　type　of　intermediates　in　chemistry,　this　one-step　＇grafting-to＇　strategy　could　be　used　to　obtain　RGO-based　materials　with　different　applications.　Copyright　©　2012　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.