The purpose of the present study is to evaluate the preparation and the structure of fraction OP-Ia and its protective effect against UV-induced photoaging through the MAPKs signaling pathway. Fractions OP-Ia and OP-Ib were prepared by enzymatic hydrolysis and purified by ultrafiltration (5 kDa) and gel chromatography (Sephadex G-25). The reducing power and superoxide radical scavenging ability were evaluated, which showed that OP-Ia had stronger antioxidant activity than OP-Ib. Next, ten peptides were identified in OP-Ia by UPLC-MS/MS. The mechanism of the anti-photoaging activity for fraction OP-Ia was investigated through the MAPKs pathway based on the HaCaT cell line. Fraction OP-Ia could inhibit the generation of ROS and the decline of cell viability induced by UV radiation, meanwhile downregulate the expression of IL-1β, IL-8, c-Jun, c-Fos, p65 NF-κB and p38 MAPK genes. Overall, the results showed that the fraction OP-Ia could be a potent component of functional foods with UV protection property.