Two-dimensional conductive metal-organic frameworks (2D c-MOFs) with high electrical conductivity and tunable structures have hold significant promise for applications in metal-ion batteries. However, the constructed of 3D interpenetrated c-MOFs for applications in metal-ion batteries is rarely reported. Herein, a 3D four-fold interpenetrated c-MOF (Cu-DBC) constructed by conjugated and contorting dibenzo[g,p]chrysene-2,3,6,7,10,11,14,15-octaol (DBC) ligand is explored as an advanced cathode material for sodium-ion batteries (SIBs) for the first time. Notably, the expanded conjugated and four-fold interpenetrating structure endows Cu-DBC with transmission channels for electrons and sufficient spacing for sodium ion diffusion. As expected, Cu-DBC cathode showcases higher specific capacity (120.6 mA h g−1, 0.05 A g−1) and robust cycling stability (18.1% capacity fade after 4000 cycles, 2 A g−1). Impressively, Cu-DBC cathode could also exhibit decent electrochemical properties at extreme temperatures (-20 °C and 50 °C). A series of in/ex situ characterizations as well as systematic theoretical calculation further reveal the sodium-ion storage mechanism of Cu-DBC, highlighting a three-electron redox process on the redox-active [CuO4] units. This work provides valuable insights for exploring and enriching 3D interpenetrated c-MOFs for applications in metal-ion batteries.