Effects of UV-B (280–315 nm) and UV-C (254 nm) at various doses upon callus of bladder campion (Silene vulgaris (M.) G. were studied. It was revealed that UV irradiation results in the decrease in arabinose and galactose residues in the silenan—the pectin fraction isolated from callus. The silenan possesses antioxidant activity (AOA) as assessed by the reaction with a stable radical. At the irradiation of callus by UV, the AOA of the silenan and the relative content of phenolic compounds in it increased; the highest increase was observed after the irradiation of callus by UV-B. Positive correlation between the AOA of the pectin fraction and an increase in phenolic compounds was revealed. This evidences that the AOA of the silenan relates to and is partially determined by phenolic compounds in its composition. The UV irradiation may be used as a tool to modify the structural features of the cell walls' polysaccharides in order to produce physiologically-active polysaccharides with desired properties.