A novel polyester UV absorber, PHA-b-PE_UV-0, was prepared by thiol-ene click reaction. The structure of PHA-b-PE_UV-0 was confirmed by ¹H-NMR, FT-IR, and UV spectrometric analyses. The anti-UV-accelerated aging performance of PHA-b-PE_UV-0 added to EVA materials was studied by estimating the tensile strength retention, contact angle and Shore hardness, and by ATR-FT-IR, XPS, and SEM analyses. The obtained results were compared with those of EVA materials with added UV-0. The results show that the addition of PHA-b-PE_UV-0 and UV-0 to EVA materials has a protective effect against UV-accelerated aging. However, PHA-b-PE_UV-0 is better than UV-0 in suppressing the increase in oxygen content and carbonyl index of the surface of EVA materials, retaining the tensile strength, and decreasing the Shore hardness. The two UV absorbers have different effects on the contact angle of the EVA materials surface. The surface contact angle of the EVA materials added with PHA-b-PE_UV-0 shows an alternating trend of first decreasing and then increasing with the UV aging time. The contact angle of the EVA materials with added UV-0 first decreases and then increases with UV aging time. However, the contact angle of the EVA materials with added PHA-b-PE_UV-0 fluctuate less. SEM analysis show that blank EVA materials begins showing a depression after 20 d of UV aging. With the increase in aging time, the concave structure gradually increases. Pits and detritus appeare on the surface of the materials with added UV-0 after 20 d of UV aging, and the amount of detritus increases after 40 d of aging. However, in the EVA materials with added PHA-b-PE_UV-0, only a small amount of raised structure is observed. It can be seen that PHA-b-PE_UV-0 has acomprehensive anti-UV-accelerated aging performance that is superior to that of UV-0.