The orientation dependence in space of Raman-active vibrations in the hexagonal structure of polyoxymethylene (POM) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. The variation of polarized intensity for the A1 and the E1 vibrational modes with respect to the POM molecular orientation is systematically studied, from both theoretical and experimental viewpoints, according to the symmetry assignments of each vibrational mode. A set of working equations including the Raman selection rules associated with the A1 and the E1 modes and the orientation distribution function are explicitly formulated and validated by means of a least-square fitting procedure on experimental data. In addition, an approach based on the introduction of orientation distribution functions is applied to quantitatively assess and compare on a statistical base the molecular orientation of two different types of electrospun POM nanofibers. Copyright © 2012 John Wiley & Sons, Ltd.