The polysaccharides (PKP-E) extracted from the pinecones of Pinus koraiensis were studied, which was fractionated using DEAE-52 cellulose and Sephadex G-100. Four novel polysaccharide fractions were obtained, which were PKP-E-1−1, -1−2, -2−1, and -2−2, respectively. The structural features were characterized using HPGPC, monosaccharide composition analysis, Congo red test, periodate oxidation, Smith degradation, FTIR and NMR spectroscopy. The results showed the 4 purified fractions were non-triple helical structured heteropolysaccharides and composed of l -rhamnose, l -arabinose, d -mannose, d -glucose, and d -galactose. The fractions were mainly linked by 1→6 or 1→ glycosidic bonds and the backbone of 4 fractions was probably composed of→2, 6)-β- d -Man-(1→ and α- d -Gal p A-(1→), which resembles pectin. Moreover, the antioxidant activities of the polysaccharides were measured by scavenging radical capacity tests. The PKP-E-2−1 was the most stable and active fraction, and the respective IC 50 for the hydroxyl and ABTS ·+ radicals were 3.0 and 23.6 mg/mL.