Phytochemical investigation of the leaves of Pometia pinnata resulted in the isolation of a new triterpenoid saponin (1), together with a known compound, kaemferol 3-O-α-L-rhamnopyranoside (2). The structure of 1 was established as 3-O-[α-L-arabinofuranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-α-Larabinopyranosyl]-hederagenin. The structure elucidation of the isolated compounds was based primarily on 1D-and 2D-NMR techniques, including 1 H and 13 C NMR spectra, DEPT, and by 2D COSY, HMQC, HMBC and TOCSY experiments.