Fourier transform infrared (FTIR) spectra of syndiotactic polystyrene (s‐PS) semicrystalline samples have been examined by using the spectral subtraction approach. For the crystalline forms including trans‐planar chains (trigonal α and orthorhombic β) a number of conformational and structural order effects, not previously described in the literature, have been identified. A method based on the results of the spectral subtraction analysis has been developed for the determination of the crystallinity degree and compared with the standard method based on the wide‐angle X‐ray diffraction patterns. The spectral subtraction analysis on FTIR spectra allows also an easy evaluation of the amount of α and β crystalline phases (often simultaneously present in melt‐crystallized samples) although both contain chains in a same conformation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1055–1066, 1997