The microstructure of solution-processed organometallic lead halide perovskite thin films prepared by the gas-assisted method is investigated with synchrotron-based techniques. Using a combination of GIWAXS and NEXAFS spectroscopy the orientational alignment of CH3NH3PbI3 crystallites and CH3NH3+ cations are separately probed. The GIWAXS results reveal a lack of preferential orientation of CH3NH3PbI3 crystallites in 200-250 nm thick films prepared on both planar TiO2 and mesoporous TiO2. Relatively high efficiencies are observed for device based on such films, with 14.3% achieved for planar devices and 12% for mesoporous devices suggesting that highly oriented crystallites are not crucial for good cell performance. Oriented crystallites however are observed in thinner films (approximate to 60 nm) deposited on planar TiO2 (but not on mesoporous TiO2) indicating that the formation of oriented crystallites is sensitive to the kinetics of solvent evaporation and the underlying TiO2 morphology. NEXAFS measurements on all samples found that CH3NH3+ cations exhibit a random molecular orientation with respect to the substrate. The lack of any NEXAFS dichroism for the thin CH3NH3PbI3 layer deposited on planar TiO2 in particular indicates the absence of any preferential orientation of CH3NH3+ cations within the CH3NH3PbI3 unit cell for as-prepared layers, that is, without any electrical poling.