Underwater superoleophobic membranes as an effective means of resisting oil stains are often subjected to cumbersome modification procedures, limited stability, and difficult expansion of assembly. To develop simple, green, stable, and scalable underwater superoleophobic films, herein, cellulose-based oil-water separators with high-efficiency oil purification were constructed by using commercial carboxymethocel (CMC) as a solute and a dimethyl sulfoxide-modified ionic liquid as a solvent. Owing to the superior dissolution, regenerability, and gelation of CMC, the metal mesh and gauze can be imparted with an excellent oleophobic ability through simple dipping, spraying, and coating of the CMC solution. As a result, these modified functionalized devices exhibit a purification capacity of more than 99.5% for various oil-water mixtures. Unexpectedly, the CMC gel coating also shields the gloves from organic solvents. Significantly, when the CMC solution is applied to an adsorption membrane, it not only endows the film with excellent oil-water separation characteristics but also enhances the adsorption amount and rate of the adsorbent. Therefore, CMC-based oleophobic materials can be widely developed and applied to a variety of fields that require oleophobic properties.