Although various superhydrophobic/superoleophilic porous materials have been developed and successfully applied to separate water-in-oil emulsions through sizesieving mechanism, the separation performance is restricted by their nanoscale pore size severely. In this study, the wettability of underoil water on fumed silica was experimentally observed and underlying mechanism was investigated by carrying out theoretical analysis and molecular dynamic (MD) simulations. Further, we present a novel, facile and inexpensive technique to fabricate underoil superhydrophilic metal felt with micro pores for separation of water-in-oil emulsions by using SiO2 nanoparticles (NPs) as building blocks. The as-prepared underoil superhydrophilic coating is closed-packed and ultrathin (the thickness is approximate hundreds of nanometers), as well as capable of being coated on metal felt with complex structures without blocking its pores. The as-prepared metal felt could adsorb water droplets directly from oil, which endowed it with the ability to separate both surfactant-free and surfactant-stabilized water-in-oil emulsions with high separation efficiency up to 99.7% even though its pore size is larger than that of the emulsified droplet. The filtration flux for separation of span 80-stabilized emulsion is up to ~4000 L • m −2 • h −1 . Its separation performance is better than most of the other traditional membranes and superwettable materials used for separation of water-in-oil emulsions. Moreover, the as-prepared metal felt retained outstanding separation performance even after 30 cycles of use, which demonstrated its excellent reusability and durability. Additionally, the distinctive wettability of underoil superhydrophilicity endued coated metal felt with superior anti-fouling properties towards crude oil. Overall, this study not only provides a new perspective on separating water-in-oil emulsion, but also gives a universal approach to develop special wettability materials.