This paper presents a way to prepare three-dimensional carbon framework (3DCF) anode material for sodium ion batteries (SIBs) and hybrid capacitors (SIHCs). Based on ethanol/sodium hydroxide electrolyte, 3DCFs are
synthesized by electrolysis combined with subsequent calcination process. The obtained 3DCFs have the unique structure with interconnected, porous structure and defective features, which facilitates the sodium ion storage. When used as anode material for SIBs, 3DCFs display high specific capacity and rate capability, and excellent long-term cyclability. We have also assembled the SIHC devices by employing the 3DCFs as anode and sodium alginate derived activated carbon (SDAC) as cathode, the optimal 3DCFs//SDAC devices display high energy density of 133.2 Wh kg−1 and high power output of 20.0 kW kg−1 within the voltage window of 0–4.0 V, as well as long-term cycling life for 4000 cycles. This work provides opens up opportunities for fabricating novel nanostructured electrode material and constructing high performance sodium ion storage devices.