Piperine is a bioactive alkaloid that possesses various health benefits and is responsible for the pungent aroma of pepper. Piperine content in whole and ground black pepper (n = 132) was analyzed by near-infrared spectroscopy (NIRS) in the 950 to 1650 nm wavelength window. Chemometric modeling using partial least square regression was performed, and outliers were checked and removed during the preparation of the calibration curve by considering sample residual variance and sample leverage. Model accuracy was evaluated with a low root-mean-square error of cross-validation (RMSECV) and a high ratio performance to deviation (RPD). The optimal model had a coefficient of determination (R 2) of 0.726, RMSECV of 0.289 g/100 g, and RPD of 1.744 for the whole black pepper. The results of R 2 , RMSECV, and RPD for the ground black pepper were 0.850, 0.231 g/100 g, and 2.424, respectively. Therefore, based on the perspective of onsite process, the proposed NIRS method can be employed for selecting abnormal samples during the inspection of black pepper raw material and for quantifying piperine contents of final black pepper product.