To　maximize　the　utilization　of　its　single-atom　thin　nature,　a　facile　scheme　to　fabricate　graphene　multilayer　films　via　a　layer-by-layer　self-assembled　process　was　presented.　The　structure　of　multilayer　films　was　constructed　by　covalently　bonding　graphene　oxide　(GO)　using　p-phenylenediamine　(PPD)　as　a　covalent　cross-linking　agent.　The　assembly　process　was　confirmed　to　be　repeatable　and　the　structure　was　stable.　With　the　π-π　conjugated　structure　and　a　large　number　of　spaces　in　the　framework,　the　graphene　multilayer　films　exhibited　excellent　electrochemical　performance.　The　uniform　ultrathin　electrode　exhibited　a　capacitance　of　41.71　μF/cm2　at　a　discharge　current　of　0.1　μA/cm2,　and　displayed　excellent　stability　of　88.9　%　after　1000　charge-discharge　cycles.　©　2015　The　Author(s).