Aim: Polyurethane-based aligners, created through photoinitiated free-radical polymerization, have been the subject of numerous studies focusing solely on their mechanical properties. In contrast, we investigate their thermomechanical properties, which are crucial for their efficacy. This paper aims to investigate the effects of different UV light exposure durations on the complex modulus of elasticity, tan delta, glass transition temperature, and the degree of conversion (DC). Methods: Aligners were printed using Tera Harz TC-85 and NextDent Ortho Flex resin with specific exposure times (2, 2.4, 3, 4, and 4.5 s for Tera Harz; 5, 6, 7, and 8 s for NextDent) and processed per manufacturer guidelines. The degree of conversion was analyzed using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy, while Dynamic Mechanical Analysis (DMA) characterized the mechanical properties (complex modulus and tan delta) and the glass transition. Results: Tera Harz TC-85 showed a higher degree of conversion (90.29–94.54%), suggesting fewer residual monomers, which is potentially healthier for patients. However, its lower glass transition temperature (35.60–38.74 °C) might cause it to become rubbery in the mouth. NextDent Orto Flex, with a higher storage modulus (641.85–794.55 MPa) and Tg (49.36–50.98 °C), offers greater rigidity and stability at higher temperatures (greater than temperature in the oral cavity), ideal for orthodontic forces, though its lower degree of conversion raises health concerns. Conclusions: Tera Harz TC 85 generally achieves higher DC and more stable polymerization across different UV exposure times than NextDent Orto Flex. Optimal polymerization times significantly impact both the mechanical and thermal properties of these dental resins, with NextDent showing optimal properties at 7 s and Tera Harz benefiting from both very short and extended exposure times.