The hydrophobic nature of the substances has served as important tools for governing the spatial behaviors of various fibrous substances depending on their affinities to oils or organic liquids. Herein, electrospun two-dimensional (2D) polyacrylonitrile (PAN) fiber mat was converted into three-dimensional (3D) mesh by hydrogen gas foaming technique using aqueous sodium borohydride (NaBH4) solution, which on heating at high temperature under a nitrogen atmosphere produced ultra-light, low density, hydrophobic 3D carbon scaffold with distinct affinities to oil phases. The fibrous materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectra. Specific surface area and porosity of the fiber were analyzed by the Brunauer-Emmett-Teller (BET) technique. The carbon scaffold exhibit dominance as absorbents for selectively separating oils such as diesel, canola oil, xylene, and n-hexane with absorption capacity from 68.71 g g(-1) to 131.33 g g(-1). More interestingly, the absorbed oils were readily collected by simple mechanical squeezing and the recovered 3D carbon scaffold could be reused for the successive absorptions. This carbon scaffold could be a versatile platform to offer a kind of efficient and selective absorbent material for absorption of oils or organic liquids from the water.