The present study investigates the yield and purity of piperine isolated from spent black pepper (Piper nigrum L.), a ‘thrown away residue’ from ayurvedic industry. The spent pepper generated from a major ayurvedic industry has been screened for the presence of high value volatiles, extracts and active principles and also a commercially acceptable process have been developed and optimized herewith to produce oleoresin and high purity piperine from this residue. Results obtained from the UV spectrophotometry and high performance liquid chromatography (HPLC) clearly suggested that purity of piperine from raw (92.54%) and spent (93.58%) peppers were close to that of a standard piperine (97.00%). A significantly higher yield of piperine (44.74%) was obtained by prewashing the oleoresin with hexane followed by recrystallization in ethyl acetate/n-hexane ratio of 60:40. The gas chromatography (GC) analysis of essential oils isolated by hydro-distillation from raw and spent pepper samples showed significant reduction in monoterpenes compared to sesquiterpenes, with an increase of β-caryophyllene content with the effect of processing. Moreover, the contents of oleoresin, piperine and essential oil in both spent and raw pepper showed that spent pepper retains 60% of valuable compounds even after industrial processing. In this way, spent pepper generated from ayurvedic industries could be utilized for value addition by development of high value oleoresin and nutraceuticals for healthcare application.