The recently developed approach of Transition Moment Orientation Analysis is employed to determine the three dimensional orientation and order of the different molecular moieties in semi-crystalline polyolefins. Based on IR transmission spectra for varying polarisation and inclination the quadratically averaged orientation distribution of the different IR transition moments is deduced. By that, the full order parameter tensor and its orientation with respect to the sample coordinate system is obtained. (C) 2011 Elsevier Ltd. All rights reserved.