In this work, the application of a new approach for quantitative analysis, originally developed for Raman spectroscopy, is extended to IR spectroscopy. The attractive features of this methodology are its simplicity and ease of use in comparison with traditional approaches. Unlike other methods, rich spectral information containing several overlapped peaks can be used in the calculations. A robust and well-conditioned calculation scheme renders precise results, which are independent of the operator's decisions. The method was applied to study the chemical compositions of homogeneous polymer blends made of polystyrene and poly(vinyl methyl ether). Raman and IR blend spectra were acquired with confocal Raman microspectroscopy and attenuated total reflection/Fourier transform infrared, respectively. The blend compositions were calculated from the corresponding vibrational spectra with the proposed strategy, and excellent agreement between those values and the true ones was found for both techniques. (c) 2005 Wiley Periodicals, Inc.