Four purified polysaccharides (COP-H, COP-U, COP-E, and COP-A) were obtained from seed cake of Camellia oleifera Abel. by hot water extraction, ultrasonic-assisted extraction, enzyme extraction, and alkali extraction, respectively. Their structural characterizations were determined, and antioxidant activities were investigated. The results of FT-IR demonstrated that the characteristic absorption bands exhibited slight difference among four polysaccharides. HLPC analysis presented that the molecular weights were calculated to be 394, 297, 462, and 429 kDa for COP-H, COP-U, COP-E, and COP-A, respectively. GC-MS analysis showed that the monosaccharide compositions were identical to four polysaccharides, while the molecular ratios exhibited significant difference. Four polysaccharides showed antioxidant activities in a concentration-dependent manner. Among four polysaccharides, COP-E showed a higher scavenging activity on DPPH, hydroxyl radical, and superoxide anion radical. These findings suggest camellia seed cake polysaccharides have potential as a natural antioxidant.