The oil of Piper pierrei C. DC. (local name Trâu nûi, Tiêu pierrei - Piper grown on the mountain) was isolated from its aerial parts by hydrodistillation. The oil was analyzed for the first time by high resolution GC, GC/MS and 13C-NMR. It contained more than 80 constituents of which 67 compounds have been identified. The major components were α-methylbenzyl cinnamate (28.0%) and an isomeric methylbenzyl cinnamate (18.1%), esters never found before.