The soluble polysaccharides from the raw materials, 20 d fermented and 40 d fermented cayenne, were extracted and separated by DEAE-Cellulose 52 column under the same conditions. The results showed that the same four polysaccharides appeared in the three periods: Neutral polysaccharide ZPS-1 and Acidic polysaccharides ZPS-2, ZPS-3, ZPS-4, and a new Neutral polysaccharide ZPS-N appeared on the 20th day and disappeared with the prolongation of fermentation time. The Neutral polysaccharide ZPS-1 continued to decrease during the fermentation process, the 20 d fermented cayenne had the highest acid polysaccharide content, and its 5 polysaccharide fractions were further purified by SephadexG-200 column chromatography, and the highest uronic acid content was the ZPS-3. The results showed that the antioxidant activity of the three Acidic polysaccharides was significantly stronger than that of the Neutral polysaccharide ZPS-1, and the uronic acid content was positively correlated with its antioxidant activity. The crude polysaccharides from the 20 d fermented cayenne had a higher antioxidant capacity, so the edible value was relatively higher.