Small and wide angle high energy x-ray scattering experiments were performed upon cooling itraconazole from the melt to investigate the structural origin of the two transitions at similar to 74 degrees C and similar to 90 degrees C observed in DSC measurements. Slight changes to the main WAXS peak at Q=1.33 +/- 0.01 angstrom(-1) were observed at 90 degrees C and are found to be inter-molecular in nature, suggesting a liquid to isotropic transition. This finding was supported by complementary wide angle neutron scattering measurements. For temperatures at and below similar to 74 degrees C two strong rings appear in the 2D-SAXS pattern at Q= 0.24 +/- 0.01 angstrom(-1) and 0,43 +/- 0.01 angstrom(-1). The SAXS spectra were further deconvoluted into sharp and broad components. A narrowing of the broad component is associated with only minor changes in the packing arrangements of the itraconazole molecules below 90 degrees C, while the appearance of the sharp component below similar to 74 degrees C is attributed to the formation of a polydomain lamellar phase. (C) 2016 Elsevier B.V. All rights reserved.