The possibility of obtaining of new polymeric salts on the basis of guanidinium and phosphonium polysulfones was investigated. Guanidinium and phosphonium polysulfones were synthesized by free radical copolymerization technique. Polysulfonylpyrrolidinium and polysulfonylpyrrolidinylphosphonium hydroxides were obtained by ion chromatography. Chemical modification of hydroxides results in new optically and biologically active polymeric guanidinium and phosphonium salts for the first time. NMR, FTIR and element analysis were used to confirm the chemical structure and element composition. New polymeric guanidinium and phosphonium salts possess optical activity and are effective in controlling bacteria, spores and fungi.