This study reports on how the degree of polymer order within a polymer/fullerene blend can be investigated by spectroscopic methods. Non-annealed blend compositions with 080 wt % fullerene content were analyzed using temperature dependent photoluminescence (PL) and room temperature spectroscopic ellipsometry (SE) measurements. To evaluate the SE data with respect to the optical order, an optical model was developed, including a lower and higher ordered polymer phase within a fullerene matrix. This was done using an effective medium approach describing the polymer by combining lower and higher ordered polymer properties (polymer-EMA). The polymer/fullerene blend was then evaluated using another EMA consisting of the polymer-EMA and the dielectric function of the disordered fullerene. The degree of optical order obtained by SE, was confirmed using another independent measurement, photoluminescence spectroscopy, according to the method of Francis C. Spano (2005). The volume fraction of the ordered polymer within the polymer-EMA was found to be between 70 and 60 vol % for fullerene contents lower than 20 wt % in the polymer/fullerene blend. Above 20 wt % fullerene, the optical order of the polymer strongly decreases all the way down to 0 vol %. In contrast to the complementary performed X-ray diffraction measurements, which address only the long-range structural order of the blends, we give quantitative information on the optical order, including information on the composition, that is, volume fractions of the higher and lower ordered polymer. The gained information on the tilt of the polymer molecules with respect to the substrate is discussed comparing XRD results from the literature with those obtained by our SE model. Finally, the developed model is used to describe the influence of the P3HT molecular weight on the optical order. Results obtained with our model were compared to the structural data and mobility data in the literature. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012