The feasibility of near infrared spectroscopy (NIRS) for discrimination between mature vinegar of different geographical origins (Taiyuan and Qingxu, China) is presented in this research. NIR spectra were collected in transmission mode in the wavelength range of 800–2500 nm. Qualitative analysis models were developed based on Principal Component Analysis (PCA) and Discriminant Analysis (DA). The prediction performance of calibration models in different wavelength range was also investigated. The best models gave a 96.3% classification of mature vinegars of the two geographical origins in the range of 800–2500 nm. The results demonstrated that NIRS technique could be used as a rapid method for classification of geographical origin of mature vinegars.