Oil-polluted water is a worldwide problem due to the increasing industrial oily wastewater and the frequent oil spill accidents. Here, we report a novel kind of superhydrophilic hybrid membranes for effective oil/water separation. They were prepared by depositing CaCO3-based mineral coating on PAA-grafted polypropylene microfiltration membranes. The rigid mineral-coating traps abundant water in aqueous environment and forms a robust hydrated layer on the membrane pore surface, thus endowing the membranes with underwater superoleophobicity. Under the drive of either gravity or external pressure, the hybrid membranes separate a range of oil/water mixtures effectively with high water flux (>2000 L m(-2) h(-1)), perfect oil/water separation efficiency (>99%), high oil breakthrough pressure (>140 kPa) and low oil fouling. The oil/water mixtures include not only free mixtures but also oil-in-water emulsions. Therefore, the mineral-coated membrane enables an efficient and energy-saving separation for various oil/water mixtures, showing attractive potential for practical oil/water separation.