Near-infrared (NIR) spectroscopy has gained increased attention for the qualitative and quantitative evaluation of textile and polymer products. Many NIR instruments have been commercialized to identify the natural and synthetic fibers; however, there is a strong need to have NIR database of these high-performance fibers to detect contraband textile materials rapidly and quantitatively. In this study, NIR spectra of PLA, Kevlar, Spandex and Sorona woven fabrics were collected and studied by several calibration models to identify the fibers. The results indicated that these four innovative fibers had been successfully distinguished by their NIR spectra in combination with preprocessing of 1/X transformation, SNV, and 2nd Savitzky-Golay derivative as well as principalcomponent-analysis (PCA-) based chemometric methods. Our promising results suggest that NIR spectroscopy is an effective technique to anticounterfeit innovative fibers.