We have shown previously that the roots of Cynoglossum pictum Ait. contain two alkaloids, but their composition was not studied. We investigated the roots of this species collected in June 1970 on the southern shores of the Crimea in the region of the Baidar Gate. The mixture of alkaloids obtained by dichloroethane extraction was separated on a column (d 2.5, h 12 cm) of alumina (Brockmann activity grade III) with mixtures of chloroform and methanol in proportions changing successively from 99:1 to 90:10, yielding two bases with Rf 0.80 and 0.09 in the chloroform-methanol (9:1) system. The base with Rf 0.80 yielded a crystalline picrate with mp 98-100°C identical with the picrate of cynoglossophine-heliosupine. Assuming the second alkaloid was an N-oxide, we reduced it with zinc dust in 5% sulfuric acid; the reduced base had Rf 0.80 in the chloroform-methanol (9:1) system and 0.54 in the benzene-diethyl ether-methanol (10:5:2) system, and its Rf value coincided with that of cynoglossophine-heliosupine under the same conditions when chromatographed with alkaloid 'markers.' Thus, we are the first to have established that the roots of Cynoglossum pictum Ait. contain two alkaloids—cynoglossophine-heliosupine and its N-oxide.