In accordance with the present invention there is provided a method for the separation of a triglycoalkaloid in which the triglycoside portion comprises -L-rhamnopyranosyl-(12gal)-O--D-glucopyranosyl-(13gal)--D-galactopyranose (or 6-deoxy--L-mannopyranosyl-(12)-O-[-D-glucopyranosyl-(13)]--D-galactopyranoside) ('an rhamnose-glucose-galactose triglycoalkaloid') from a triglycoalkaloid in which the triglycoside portion is -L-rhamnopyranosyl-(12glu)-O--L-rhamnopyranosyl-(14glu)--D-glucopyranose ('a rhamnose-rhamnose-glucose triglycoalkaloid') in a mixture containing both, the method comprising the steps of: Combining the mixture with a portion of alcoholic solvent; Causing or allowing a substantial portion of the rhamnose-rhamnose-glucose triglycoalkaloid to dissolve, thereby generating an alcoholic solution substantially of the rhamnose-rhamnose-glucose triglycoalkaloid, and a solid substantially comprising the rhamnose-glucose-galactose triglycoalkaloid; and Separating the solid substantially comprising the rhamnose-glucose-galactose triglycoalkaloid from the solution substantially of the rhamnose-rhamnose-glucose triglycoalkaloid.