The complex orientation dependence in space of Raman active vibrations in the orthorhombic structure of polyethylene (PE) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. Building upon the symmetry assignment of these vibrational modes, we systematically studied, from both theoretical and experimental viewpoints, the changes of polarized intensity for the Ag and the B2g + B3g vibrational modes with respect to PE molecular orientation. After explicitly expanding the Raman selection rules associated with the Ag and the B2g + B3g modes, introducing them into general expressions of the orientation distribution function, and validating them by means of a least-square fitting procedure on experimental data, we compare here two mesostructural models for a highly crystallized and self-aligned PE fiber structure. Stereological arguments are shown concerning the arrangement of orthorhombic fibrils in such a sample that unfold the correct values of five independent Raman tensor elements for orthorhombic PE. Copyright © 2010 John Wiley & Sons, Ltd.