The PVA-based carbon nanofibers with honeycomb-like carbon porous structure were successfully prepared by electro-blown spinning (EBS), pretreatment and carbonation processes. PVA was used as the carbonized polymer while PTFE was used as the sacrificial polymer. The carbon nanofibers with various pore sizes and distribution were prepared by varying the amount of PTFE loading in the spinning solution and optimizing carbonized parameters. The honeycomb-like carbon nanofibers were investigated by scanning electron microscopy (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectrum and low temperature nitrogen adsorption. It was found that specific surface area and pore volume could reach 591.33 m(2) g(-1) and 0.58 cm(3)/g, respectively, and large amount of micro-, meso- and macro-pores existed in this kind of porous carbon fiber when the PVA/PTFE was 1:15. This porous carbon nanofiber with special structure and high yield may realize the applications in the fields of adsorption, ion exchange, catalyst supports, etc., and the prepared method has a great industrialization potentiality. (C) 2016 Elsevier Inc. All rights reserved.