In this study, GO-MOFs derived rGO coating/sandwiching Co3O4 composites (denoted as rGO/Co3O4) are fabricated by employing a temperate coprecipitation method with ZIF-67 rhombic dodecahedron as a template and GO as a substrate. In these composites, nanoporous and rGO coating (denoted as rGO@Co3O4)/sandwiching (denoted as Co3O4-rGO-Co3O4) structures are designed, which endow the composites with strong potential application as electrode materials for lithium-ion batteries (LIBs) and supercapacitors (SCs). Here, the as-prepared rGO@Co3O4 and Co3O4-rGO-Co3O4 composites not only exhibit outstanding lithium storage performances with high initial discharge specific capacities (1451 and 1344mA h g−1 at a current density of 100mAg−1), excellent cycling stabilities (above 96% and 95% retention after 100 cycles) and admirable rate capabilities (328 and 450mA h g−1 at a current density of 2000mAg−1), but also display superior pseudocapacitive properties with high specific capacitance (546Fg−1), remarkable rate capability and brilliant cycling stability (90% of initial capacitance retention at 5Ag−1 after 10000 cycles). The remarkable porous architecture and electrical conductivity enables GO-MOFs derived transition metal oxide composites to be promising electrode materials for next generation LIBs and SCs.