Two glycoalkaloids previously unreported in Solanum demissum have been isolated and identified as commersonine and neotomatine. Solanum demissum has been reported to contain demissine and tomatine. We now wish to report the isolation and characterization of two glycoalkaloids previously unreported from S. demissum in accession No P.I. 205514. The glycoalkaloid fraction of S. demissum foliage was isolated by basic precipitation using standard techniques. TLC of this fraction indicated the presence of four compounds, two of which were readily identified as demissine and tomatine on the basis of TLC and GC/MS characterization of the aglycones. The aglycones of the glycoalkaloids were identified by GC/MS following hydrolysis in hydrochloric acid in methanol; the structure of the carbohydrate moieties were determined by permethylation analysis. One of these unknown compounds was identified as commersonine, a glycoalkaloid recently isolated from S. commersonii [2]. The remaining glycoalkaloid which we have named neotomatine, was present in relatively small quantities. It was characterized as a tetraose derivative (1) of tomatidine, the tetraose moiety being identical to the tetraose (commertetraose) of commersonine. Therefore, S. demissum has a more complex glycoalkaloid composition than had previously been reported, resulting from the commertetraose moiety in combination with the aglycones that were previously identified in the lycotetraose glycoalkaloids of this species. This brings to three the number of Solanum species in which the commertetraose moiety has been found.