The simultaneously oleophobic/hydrophilic coatings are highly desirable in antifogging, oil-water separation, and detergent-free cleaning. However, such coatings require special chemical structure, i.e, perfluorinated backbone and polar end groups, and are too expensive for real-life application. Here, we have developed an UV-based photochemical approach to make nanometer-thick perfluoropolyethers without polar end-groups, which are not intrinsically simultaneously oleophobic/hydrophilic but cost-effective, become simultaneously oleophobic/hydrophilic. The contact angle, ellipsometry, and X-ray photoelectron spectroscopy (XPS) results indicated that the UV irradiation results in the covalent bonding between the polymer and the substrate, which renders more ordered packing of polymer chains and thus the appropriately small interchain distance. As a result, the small water molecules penetrate the polymer network while large oil molecules do not. As a result, the oil contact angle is larger than the water contact angle and the coating shows the simultaneous oleophobicity/hydrophilicity. Moreover, we also demonstrated that this nanometer-thick simultaneously oleophobic/hydrophilic coating has improved long-term antifogging performance and detergent-free cleaning capability and is mechanically robust. The photochemical approach established here potentially can be applied on many other polymers and greatly accelerate the development and application of simultaneously oleophobic/hydrophilic coatings.