The invention relates to a radiation curable release and transfer printing composition which comprises the following components in parts by weight: 50-70 parts of at least one of fluorine-containing oligomer and silicon-containing oligomer, 20-40 parts of at least one of a fluorine-containing monomer and a silicon-containing monomer, 4-8 parts of release aids and 5-9 parts of a photoinitiator. Application of the composition comprises the following steps: by taking a PET (Polyethylene Terephthalate) base membrane as a substrate, coating the PET base membrane by the release and transfer printingcomposition, baking, carrying out mold pressing and radiation curing, separating by using pressing rollers, and carrying out air cold coiling, thereby obtaining a radiation curable multifunctional release and transfer printing membrane. Due to UV (Ultraviolet) curing and a pure solid content, the radiation curable release and transfer printing composition is free of solvent and energy-saving andenvironmentally friendly, a fluorine-containing or silicon-containing component can be cross-linked and cured in a system, the obtained release membrane is long-lasting in release effect, the temperature resistance and the size stability of the membrane are remarkably improved when being compared with those of a base membrane, and due to the lubrication property of the composition, the release membrane has scratching resistance and can be repeatedly used for multiple times at a high temperature.