The compositions of leaf and stem essential oils from Vietnamese Piper umbellatum L. has been investigated by combination of chromatographic [GC(RI), GC-MS, CC] and spectroscopic techniques (GC-MS, C-13 NMR). Thirty-nine compounds have been identified, they accounted for 99.7% and 99.6%, respectively, of the whole compositions, dominated by safrole (76.2 and 66.0%). Stem oil contained fair amounts of (2E,4E)-decadienoic acid methyl ester, (2E,4E,6E)-decatrienoic acid methyl ester and (2E,4E)-N-isobutyl-2,4-decadienamide, reported for the first time in P. umbellatum essential oils and rarely found in the plant kingdom. The stereochemistry of all the double bonds was ascertained by using C-13 NMR data.