In this study, a novel hybrid structure of homogeneously distributed Co3O4 nanograins on a hexagonal Co(OH)(2) plate is synthesized using a one-pot hydrothermal reaction of ZIF-67. Particularly, because Co-containing ZIF-67 serves as a self-template during the hydrothermal conversion process, various-sized hybrid structures can be prepared using different sizes of ZIF-67 as the precursor material. Owing to their unique structural features, the obtained hybrids effectively boost the electrochemical activation of Co3O4 and Co(OH)(2) by preventing aggregation issues. Among the various-sized architectures, large-sized structure exhibits the highest capacity of 184.9 mAh g(-1) (at 1 A g(-1)) in aqueous 1 M KOH electrolyte, indicating that the electrochemical performance is improved as the size of hybrid increases. Furthermore, multifarious all-solid-state hybrid supercapacitors are successfully fabricated with various-sized Co3O4/Co(OH)(2) hybrids as the positive electrode and mesoporous plasma-reduced graphene oxide as the negative electrode. Notably, the as-prepared hybrid supercapacitors deliver a maximum energy density of 37.6 Wh kg(-1) and peak power density of 47 kW kg(-1) with excellent cycling stability (91% capacity retention after 5000 cycles).