A new synthetic method of preparing poly(ester-beta-sulfone)s from sodium formaldehyde sulfoxylate (SFS) and a diacrylate monomer (1,6-hexanediol diacrylate or 1,9-nonanediol diacrylate) in aqueous solution was studied. The structures of poly(ester-beta-sulfone)s were identified and their crystal morphology analyzed. It turned out that the poly(ester-beta-sulfone)s crystals were ring-shaped spherulites. The melting point of both poly(ester-beta-sulfone)s was 97 degrees C and 116 degrees C, respectively. The thermal degradation temperature in both cases was close to 281 degrees C.