The present disclosure provides an acryloyloxy-terminated polydimethylsiloxane (AC-PDMS)-based thin-film composite (TFC) membrane, and a preparation method and use thereof. In the preparation method, a simple ultraviolet (UV)-induced monomer polymerization strategy based on high UV reactivity among acryloyloxy groups is adopted to prepare the AC-PDMS-based TFC membrane. The high UV reactivity among AC-PDMS monomers can induce the rapid curing of a casting solution to enable the formation of an ultra-thin selective layer and the inhibition of pore penetration for a substrate. By optimizing a UV wavelength, an irradiation time, and a polymer concentration, the prepared AC-PDMS-based TFC membrane has a CO2 penetration rate of 9,635 GPU and a CO2/N2 selectivity of 11.5. The UV-induced monomer polymerization strategy based on material properties provides a novel efficient strategy for preparing an ultra-thin PDMS-based membrane, which can be used for molecular separation.