In the present work, fresh and spoiled wine samples from three wines produced by different companies were studied using Fourier transform infrared (FTIR) spectroscopy. We analyzed the physicochemical property change in the process of spoilage, and then, gave out the attribution of some main FTIR absorption peaks. A novel determination method was explored based on the comparisons of some absorbance ratios at different wavebands although the absorbance ratios in this method were relative. Through the compare of the wine spectra before and after spoiled, the authors found that they were informative at the bands of 3 020～2 790, 1 760～1 620 and 1 550～800 cm-1. In order to find the relation between these informative spectral bands and the wine deterioration and achieve the discriminant analysis, chemometrics methods were introduced. Principal compounds analysis (PCA) and soft independent modeling of class analogy (SIMCA) were used for classifying different-quality wines. And partial least squares discriminant analysis (PLS-DA) was applied to identify spoiled wines and good wines. Results showed that FTIR technique combined with chemometrics methods could effectively distinguish spoiled wines from fresh samples. The effect of classification at the wave band of 1 550～800 cm-1 was the best. The recognition rate of SIMCA and PLS-DA were respectively 94% and 100%. This study demonstrates that Fourier transform infrared spectroscopy is an effective tool for monitoring red wine’s spoilage and provides theoretical support for developing early-warning equipments.