To realize the high-value utilization of discarded Ginkgo biloba exocarp (GBE) and explore the application potential of its antioxidant active substances, GBE was used as the raw material in this study. With total antioxidant capacity taken as the evaluation index, central composite design-response surface methodology was adopted to optimize the ultrasound-assisted extraction process of antioxidants from Ginkgo biloba exocarp (AGBE). Liquid chromatography coupled with high-resolution mass spectrometry was applied for the qualitative analysis of active components, and the in vitro antioxidant activity was systematically evaluated. The optimal extraction parameters of AGBE were determined as follows: ultrasonic temperature 59 ℃, ultrasonic time 49 min, ultrasonic power 312 W, and liquid-to-solid ratio 21:1 (mL·g-1). Under these conditions, the total antioxidant capacity reached 3.10±0.02. A total of 211 compounds were identified from AGBE, among which organic acids (43.70%), phenolic compounds (20.68%) and terpenoids (16.60%) were the dominant active components. Moreover, (2R,3S)-euscaphic acid and 4-hydroxycoumarin were discovered in GBE for the first time. AGBE exhibited excellent scavenging effects on DPPH radical, ABTS radical and superoxide anion radical, with IC?? values of 215.60 μg·mL-1, 48.19 μg·mL-1 and 823.00 μg·mL-1, respectively, and the ferric ion reducing power was 7.46 mmol·mg-1. This study can provide theoretical basis for the further development of functional active components in GBE and the research and development of natural antioxidant products.