The invention discloses a release agent, a release film, a composite film and an ink-jet printing medium, preparation methods of the release agent, the release film, the composite film and the ink-jetprinting medium, and an application of the ink-jet printing medium. The release agent comprises the following components in parts by weight: 5-7 parts of polyvinyl alcohol, 1-2 parts of silicon dioxide, 4-8 parts of titanium dioxide, 5-10 parts of waterborne polyurethane, 5-10 parts of emulsion wax, 0.5-1.5 parts of a wetting agent, and water, wherein the solid content of the release agent is 15-30%. The preparation method of the release agent comprises the following steps: preparing 8-12% of polyvinyl alcohol water solution, 10-15% of a silicon dioxide dispersion liquid and 20-40% of a titanium dioxide dispersion liquid, and then performing uniform mixing with other components to obtain the release agent. The release film is obtained by coating the release agent on a base material, and performing drying, cooling and stripping, wherein the usage amount of the release agent is 100-130 g/m<2>. The composite film comprises a polymer base film and a release film. The ink-jet printing medium comprises a composite film and a transparent ink-absorbing coating. The release film and the polymer base film have moderate adhesive force, the release effect is good, and the ink-jet printing medium can be identified during printing.