We reported a one-step in-situ electrochemical route to synthesize 3D aerogel electrode materials including graphene and hexagonal CeO2 composites. The graphene/CeO2 aerogel can be formed via freeze-drying graphene/CeO2 colloidal solution that was obtained by electrochemical exfoliation of graphite anode and in-situ deposition of CeO2 nanoparticles on graphene sheets in mixing electrolyte of (NH4)(2)SO4/Ce(NO3)(3) and (NH4)(2)SO4/(NH4)(2)Ce(NO3)(6). The as-obtained CeO2 nanoparticles were closely contacted with graphene, which can enhance the synergistic effect between graphene and CeO2. It is interesting that the as-obtained CeO2 products possessed hexagonal crystal structure that was rarely reported. The Faradaic reactivity of the graphene/CeO2 composites as supercapacitor was enhanced with the increase of the concentration of Ce salts in initial electrolyte. The introduction of CeO2 to graphene electrode can lead to the presence of additional pseudocapacitance besides the electric double-layer capacitance. This simple one-step in-situ electrochemical route can be extended to synthesize various graphene/metal oxide aerogel electrode materials for electric energy storage. (C) 2015 Elsevier Inc. All rights reserved.