A novel conductive composite thin film was prepared for the first time by hybridization between polybenzoxazine (PBZ) having high heat resistance property and conductive graphene. Mechanically robust conductive graphene/PBZ composite thin films could effectively be prepared by a simple thermal treatment, which simultaneously induces reduction of graphene oxide (GO) and crosslinking reaction of benzoxazine monomer. Graphene sheets seem to be uniformly dispersed up to 3 wt% graphene content in the composite thin film as shown in the results of chemical/crystal structural and morphological analyses. This efficient route for making graphene/PBZ composite thin film would provide simultaneous improvement of mechanical property as well as electrical conductivity.