Three new pyrrolidine alkaloids, peripentonine A-C ( 2- 4), one known pyrrolidine alkaloid, peripentadenine ( 1), and one novel indolizidine alkaloid, mearsamine ( 5), were isolated from the leaves of Peripentadenia mearsii and their structures determined by 1D and 2D NMR spectroscopy. Peripentonines A ( 2) and B ( 3) were isolated as a 1:1 mixture of inseparable diastereomers. Mearsamine ( 5) contains a novel tricyclic ring system. Peripentadenine and peripentonines A/B and C showed receptor binding affinity for the human delta-opioid receptor with IC 50 values of 11.4, 69.2, and 30.9 microM, respectively. Mearsamine did not bind to the delta-opioid receptor.