Separating oil/water emulsions is significant for the ecosystem and the petroleum and processing industry. To this end, we prepared an underwater superoleophobic membrane inspired by unique wettability of the fish scales. This membrane was fabricated by a facile vacuum filtration process of sepiolite nanofibers and chitosan, and after the cross-linking via glutaraldehyde, a self-standing membrane was obtained. The as-prepared membrane exhibited excellent capability of separating both the surfactant-free and surfactant-stabilized oil-in-water emulsions with high efficiency. This sepiolite fibrous membrane offers a convenient, reliable and efficient way for the large-scale de-emulsification process.