Background: Pectins are a class of acidic polysaccharides with complex structures. Different pectin molecules are composed of different domains, which have an important impact on their biological activity. Objective: This study aimed to determine the structural features and the antioxidant activities of the pectic polysaccharides isolated from Veronica peregrina L. Methods: The polysaccharide was isolated from Veronica peregrina L by water extraction and fractionated by ion exchange chromatography and gel permeation chromatography. The structure features of the pectic polysaccharides were determined by Fourier transform infrared spectroscopy (FT-IR) and Nuclear magnetic resonance (NMR). The antioxidant activities was evaluated by the DPPH, OH and ABTS radical scavenging ability. Results: WVPP-A2b and WVPP-A3b, with molecular weights of 48.7x10(4) and 77.6x10(4) kDa, respectively, contained homogalacturonan (HG), rhamnogalacturonan I (RG-I), and rhamnogalacturonan II (RG-II) domains with a mass ratio of 2.08:2.64:1.00 and 3.87:4.65:1:00, respectively. The RG-I domain contained an arabinogalactan II backbone and arabinans consisting of t-Araf, (1.5)-alpha-Araf, and (1.3,5)-alpha-Araf. WVPP-A3b also contained short chains consisting of the [t-Araf-(1.5)-alpha-Araf-(1 ->] structural unit. WVPP-A3b showed stronger ability to scavenge DPPH, hydroxyl, and ABTS radicals, which was potentially associated with its high content of galacturonic acid and presence of the HG domain. Conclusion: The results provide information for enhancing knowledge of the structureactivity relationship of pectic polysaccharides from V. peregrina and their potential application in the healthcare food field.