<jats:p>From cell suspension cultures of Rauwolfia serpentina grown in an optimized production medium for the glucoalkaloid raucaffricine, a novel glucoalkaloid was isolated and identified as 17-O-acetyl-21-O-β-ᴅ-glucopyranosyl-ajmaline (acetylrauglucine). This alkaloid is formed in very small amounts (< 5 × 10<jats:sup>-4</jats:sup>%). The biogenetically related N<jats:sub>α</jats:sub>-demethylated base (acetyl-nor-rauglucine) and the deacetyl product rauglucine have also been detected in culture extracts. In addition 21(.R)-(β-D-glucopyranosyl)-hydroxy-sarpagan-17-al has been isolated and identified as an artifact which originates from raucaffricine.