HypothesisSuperhydrophobic membranes with opposite wettability toward water and oil are able to separate water-in-oil emulsions. By constructing porous and hierarchal-structured superhydrophobic coating on filter paper, we hope a quick separation process could be achieved due to the acceleration of both demulsification and penetration process. ExperimentsHere, superhydrophobic coatings were prepared by simply spraying environmental and cost-effective acrylonitrile-butadiene-styrene copolymer (ABS) colloid in dichloromethane onto filter paper. The morphologies and wettability of the obtained coatings were carefully studied. Moreover, the separation performances in dealing with various surfactant-stabilized water-in-oil emulsions (SSWOE) were also investigated to verify our hypothesis. FindingsThe morphologies of the ABS coatings varied with its weight concentration in dichloromethane and they changed from porous and plain surface into porous and hierarchal-structured surface. Besides, the hydrophobicity of the above coatings varied form hydrophobic to superhydrophobic. Moreover, the resulted superhydrophobic membranes show great separation capability in separating various span 80-stabilized water-in-oil emulsions with oil filtrate purities larger than 99.90% and huge penetration fluxes whose maximum is over 13,000L/(m2h). Thus, we envision that such membrane can be a practical candidate in dealing with water-in-oil emulsions to obtain pure oils.