The invention relates to a super-hydrophilic and underwater super-oleophobic coating, as well as a preparation method and application thereof. According to the invention, an organic/inorganic hybrid sol preparation method and a surface coating method are adopted, an organic/inorganic hybrid coating containing zwitter-ion groups with a certain thickness is constructed on the material surface, and is prepared through mixing alkoxy silane functionalized glycine betaine type zwitter-ion compound and silicon dioxide particles with other auxiliaries and performing hydrolysis, coating and thermal treatment. The functional coating provided by the invention is super-hydrophilic in air and super-oleophobic underwater; as the glycine betaine type zwitter-ion compound simulating the cell outer membrane molecular structure is introduced in the prepared super-hydrophilic underwater super-oleophobic coating, the prepared functional coating has the self-cleaning function, the antifogging function, the underwater oil resistance function, and the like, and has excellent bioadhesive resistance; the coating, the method and the application thereof have the advantages that the technology is simple, raw materials are easy to obtain, the equipment is simple, the cost is low, and the coating can be large-area prepared.