Abstract:1-Carbobutoxy-β-carboline, N9-formylharman, 1-carboethoxy-β-carboline, 1-carbomethoxy-β-carboline, per- lolyrine, harman and norharman were isolated from the rhizorna of Polygala tenuifolia. The structures were elucidated on the basis of spectroscopic studies and chemical evidence. 1-carbobutoxy-β-carboline has not been seported before.