Graphene/carbon fiber(CF)/poly(vinylidene fluoride) (PVDF) conductive composite materials were prepared by co-solvent method. GO was stably dispersed in H2O/ N,N-dimethylformamide (DMF) (1∶9, volume ratio) component solvent. After sonication, a clear stable brown solution was prepared without any visible aggregation. Changes in the internal structure of the graphene/PVDF composites was demonstrated by scanning electron microscopy (SEM).The interaction between the graphene and carbon fiber was observed transmission electron microscope (TEM). It is found that oxidized carbon fiber (CF) is helpful to significantly improve the conductivity of graphene /PVDF composites by 3 orders of magnitude than that of the graphene /PVDF composites. Oxidized CF/graphene/PVDF composites show a positive temperature coefficient (PTC) behavior. The negative temperature coefficient (NTC) effect was eliminated after mixing of oxidized CF and graphene. The reasons of the above differences and phenomena were analyzed by SEM.