Freestanding boron nitride nanosheet (BNNS) films with designed structures are first fabricated by chemical vapor deposition (CVD) methods. As-prepared freestanding BNNS films exhibit outstanding hydrophobicity and lipophilicity properties. Such brilliant behaviors make them applicable in oil/water separation with very high fluxes up to 1 200 000 L m-2 h-1 bar-1 and excellent separation efficiencies (ppm level in terms of the water content in the filtrate).