The near-infrared spectra (NIR) of polyamide 6 (PA 6), poly(vinyl chloride) (PVC), and polychlorotrifluoroethylene (PCTFE) were measured. The tentative assignment of the overtone and combination frequencies was made with curve fitting calculations and local mode theory. Anharmonicity correction and mechanical frequency were determined from a Birge-Sponer plot. Tentative assignments of stretch overtone frequencies of CH2 NH, and CO functional groups of PA 6 and CH2 and CH functional groups of PVC were made. Anharmonicity corrections of 55, 61, and 20 cm(-1) were obtained for CH2 NH, and CO stretch modes of PA 6, respectively, and of 60 and 66 cm(-1) for CH2 and CH stretch modes of PVC, respectively. The local mode model seems to be adequate to interpret the origin of the bands observed in NIR spectra of PA 6 and PVC. Anharmonicity corrections of 33, 19, and 16 cm(-1) were obtained, respectively, for CF, asymmetrical CF2, and symmetrical CF, stretch of PCTFE functional groups.