This content introduces a novel Ultraviolet (UV)-shielding material, Zn2Al-MADS-LDH (MADS-LDH), which was synthesized through co-precipitation method to insert sodium dodecyl diphenyl ether disulfonate (MADS) into the interlayer of Zn2Al-LDH layered double hydroxide (LDH), to improve the photoaging resistance of polyvinyl chloride (PVC). The characterization results indicated that MADS-LDH had a host-guest interaction between the LDH host layer and MADS guest anion, and it exhibited superior UV absorption capabilities than Zn2Al-CO3-LDH (CO3-LDH) and a broader absorption spectrum compared to MADS. A series of LDHs/PVC film composite materials containing LDHs nanosheets were prepared by incorporating the prepared LDHs into a PVC matrix via a solvent casting method. As expected, the MADS-LDH/PVC film composite materials exhibited enhanced photoaging resistance. The results of photoaging tests indicated that MADS-LDH inhibits the rate of carbonyl generation during photoaging of MADS-LDH/PVC film composite materials, resulting in a decrease in the carbonyl index (ΔCl) and relative degradation rate (RDR) compared to pristine PVC film and CO3-LDH/PVC film composite materials. Furthermore, the study evaluated the influence of different UV light wavelength ranges, such as UVB (280~315 nm), UVC (200~280 nm), and UV (200~400 nm), on the aging performance of PVC film and LDHs/PVC film composite materials. The results demonstrated that UV had the highest aging effect on PVC composite films, followed by UVC and UVB. Therefore, the MADS-LDH is a highly efficient and promising UV-shielding material with excellent potential for wide applications in the field of PVC.