Thermoplastic poly urethane (TPU) is a diblock copolymer which naturally phase segregates into thermodynamically incompatible hard (H) and soft (S) segments. The size of the segments and their spatial distribution can significantly affect the microstructure and mechanical properties of the material. In this paper, we investigated the effect of duration of exposure to ultrasound on the solution prior to film formation on the final film properties. The response variable for the study was primarily mechanical properties of the TPU thin films fabricated via a solution route utilizing tetra hydro furan as a solvent. The times of sonication were varied between 30 min and 90 min, while all films were fabricated at average thickness of 20 ± 5 μm. The mechanical tests have been conducted at two different displacement rates of 5 and 10 mm/min. Our results indicated that (relative to untreated TPU) ultrasound tends not to deteriorate the fracture strength, strain and yet improve the fracture toughness. We attribute these results to subtle events at the H and S segment/domain levels. To further understand these microstructural variations, we conducted differential scanning calorimetry scan tests between 25 °C and 200 °C at 5 °C/min on untested and tested TPU samples of all types. This data showed a delicate sonication time dependent trend and has been interpreted in conjunction with our mechanical test data. Transition temperatures, enthalpies, and specific heat capacities have been computed for these cases.