Heliotropium crassifolium Boiss, (Boraginaceae) from a population of Ilam, western region of Iran was studied for pyrrolizidine alklaoids (PAs). Four alkaloids have been identified: europine 1, europine N-oxide 2 and a new pyrrolizidine alkaloids ilamine 3 and its N-oxide 4, respectively. Their structures were elucidated by IR, 1H-NMR and EIMS data.