The major alkaloids in piper species traded in South Indian markets as the Ayurvedic drug, Pippali, have been studied using a rapid HPLC-based method. Piper longum is the accepted botanical source of Pippali. Bengaluru and Chennai markets contained mixtures of closely related species, Piper peepuloides and Piper sylvaticum . Chemical analysis showed that these sam-ples do not contain the alkaloid piperine present in Piper longum fruits. Market samples from Trissur were identified as Piper longum and piperine was detected as one of the major alkaloids. All the samples contained pellitorine, another alkaloid reported in most peppers of the genus Piper . The two types of Pippali can therefore be easily differentiated on the basis of their HPLC profiles.