Here we report a study of the polymer chain/nanocrystal ordering in thin films (nanolayers) of regioregular poly(3-hexylthiophene) (P3HT) and blends of P3HT with a soluble fullerene derivative. A detailed analysis has been made of two dimensional (2D) grazing incidence X-ray diffraction (GIXRD) measurements with synchrotron radiation. P3HT samples with three different levels of regioregularity (RR) were synthesized and used to investigate the influence of RR on the chain ordering in thin films. Blend films were also prepared to investigate the influence of fullerene molecule addition on chain ordering. For the analysis, one dimensional (1D) GIXRD patterns were extracted from the 2D images for varying azimuthal angles, allowing information to be obtained for chain ordering in both the out-of-plane (OOP) and in-plane (IP) directions. These results show that the degree of P3HT chain ordering is strongly affected by RR, and that thermal annealing improves chain ordering in the OOP direction. This observation is in good agreement with high resolution transmission electron microscope measurements of film nanomorphology.