Polypodoside A, a novel intensely sweet constituent of the rhizomes of Polypodium glycyrrhiza, was established by spectral and chemical methods as 26-O-alpha-L-rhamnopyranosyl-polypodogenin-3-O-alpha-L-rhamnopyran osyl- (1----2)-beta-D-glucopyranoside [1]. At the doses tested, this isolate was not acutely toxic for mice and was nonmutagenic with Salmonella typhimurium strain TM677. This compound was rated by a human taste panel as exhibiting 600 times the sweetness intensity of a 6% w/v aqueous sucrose solution.