Cellulose is a natural material with dissolution-regeneration property and numerous hydrogen bonds in the molecule. By utilizing these properties, this paper reported the development of a multi-functional fabric consisting of cellulose and commercial cotton fabric. The morphology, mechanical and thermal properties along with the oil-water separation performance of the developed material were studied. The results showed that the cellulose dissolved in NaOH/urea solution was regenerated in a salt solution, and attached tightly onto the cotton fabric, forming a sandwich structure for the material. Such modification significantly enhanced the strength, thermal stability and hydrophilic performance of the fabrics. Interestingly, the prepared material exhibited a unique underwater oleophobic performance, and had the capability to separate highly emulsified oilwater mixtures. The relatively low cost for the material preparation, enhanced mechanical property and high separation performance distinguished the developed material a suitable candidate for the separation of emulsified oil from water in practical applications.