A new naphthoquinone (I) and new monoterpenoid (II) were isolated from the stems of Plumbago zeylanica, and their structures were determined on the basis of 2D NMR spectroscopy. The absolute configuration of II was established by synthesis of its enantiomer. I exhibited potent inhibitory activity against nuclear factor κB (NF-κB), equivalent to that of parthenolide, a known potent inhibitor of NF-κB.