Polysaccharides from hemp seeds exhibit antioxidant activities in vitro and in vivo. However, crude polysaccharide quality is often low owing to the presence of fibres and pigment impurities, which are difficult to eliminate in the hemp seed shell. In this study, crude polysaccharides from hemp kernels (HKP) were obtained by hot water extraction and separated by membrane ultrafiltration into eight fractions with different molecular weights. Total antioxidant capacity and free radical scavenging (DPPH) assays were performed to evaluate the antioxidant activities of HKP and the fractions in vitro. The structural characteristics of HKP were determined using various analytical techniques. The Fe³⁺-reducing power of HKP was 7.65 ± 0.22 μmol/g, and HKP possessed the highest DPPH radical-scavenging rates (94.30 ± 2.27%), similar to 5 mg/mL Vitamin C (Vc), which had a rate of 95%. The HKP was an acidic polysaccharide with a low molecular weight (4.21 ± 0.12 kDa). The monosaccharide composition indicated that HKP primarily comprised mannose, ribose, glucuronic acid, galacturonic acid, glucose, galactose, arabinose, and fucose in a molar ratio of 0.96:1.95:8.27:0.98:9.46:1.69:6.10:2.82. The molar mass of HKP was distributed widely in a triple helical conformation. This study provides a scientific basis for further research on the use of hemp polysaccharides.