Non-solvent assisted electrospinning was proposed for fabricating Polymethylmethacrylate (PMMA) microspheres and fibers with a hollow core and porous shell, which could be used for oil adsorption and oil/water separation. Propanediol was chosen as the non-solvent because of its high surface tension and viscosity as well as large phase separation tendency with polymer, which was beneficial to the formation of both the hollow core and porous shell during the electrospinning. With the increase of the polymer solution concentration, the microsphere gradually evolved to the bead-on-string geometry and finally to a continuous fiber form, indicating the transition from electro-spraying to electrospinning. The hollow core and dense surface pores enhanced the hydrophobicity, oleophilicity, permeability, and specific surface area of the fibers, and hence imparted the fibrous mat a high oil adsorption capacity. When the porous hollow microspheres were electro-sprayed onto the stainless steel mesh followed by the PDMS modification, the modified mesh became super-hydrophobic and super-oleophilic with the contact angle of 153 degrees and sliding angle of 4 degrees. The as-prepared mesh showed rapid oil/water separation with high efficiency and excellent recycling performance. The flux for separation of oil/water mixture could reach as high as 11,000 Lm(-2) h(-1). This facile non-solvent assisted electrospinning method provides a new avenue for preparation of multifunctional porous materials which possess potential applications in large-scale oil/water separation. (C) 2018 Elsevier B.V. All rights reserved.