The chemical investigation of Heliotropium transalpinum var. transalpinum Vell. (Boraginaceae) led to the isolation of transalpinecine (1), a novel pyrrolizidine alkaloid, in addition to known alkaloids subulacine (1b-2b-epoxy-1a-hydroxymethyl-8a-pyrrolizidine) (2), and 1a-2a-epoxy-1b-hydroxymethyl-8a-pyrrolizidine (3). The structures of the isolated compounds were elucidated based on spectroscopic data and theoretical calculations.