Hierarchical porous hollow carbon nanospheres (HCNSs) were fabricated directly from raw biomass via a one-step method, in which HCNSs were obtained by thermal treatment of raw biomass in the presence of polytetrafluoroethylene (PTFE). The HCNSs possess coupling merits of uniformly distributed hollow spherical architectures, and high specific surface area, abundant accessible/open micropores and reason-able mesopores, the HCNS-based electrodes deliver high electrochemical capacitance. The formation mechanisms of pores and hollow core-shell structures were explored thoroughly, it is found that the key to the formation of hollow core-shell structure is the onset-pyrolysis temperature difference between raw biomass and PTFE. Moreover, the content of silica had significant effects on the textures of HCNSs, and HCNS with the largest SSA of 1984 m(2)/g was obtained. Accordingly, a possible mechanism of HCNSs formation was proposed here, where PTFE acted as the pore creation and nucleation agents and raw biomasses were the primary carbon precursors. (C) 2020 Elsevier Inc. All rights reserved.