Investigating the impact of thermal and mechanical loading on the force generation of orthodontic aligners made from various thermoplastic materials and different compositions. Five distinct materials were utilized including, three multi-layer (Zendura FLX, Zendura VIVA, CA Pro) and two single-layer (Zendura A and Duran). A total of 50 thermoformed aligners (n = 10) underwent a 48-hour ageing protocol, which involved mechanical loading resulting from a 0.2 mm facial malalignment of the upper right central incisor (Tooth 11) and thermal ageing through storage in warm distilled water at 37°C. The force exerted on Tooth 11 of a resin model was measured both before and after ageing using pressure-sensitive films and a biomechanical setup. Before ageing, pressure-sensitive films recorded normal contact forces ranging from 83.1 to 149.7 N, while the biomechanical setup measured resultant forces ranging from 0.1 to 0.5 N, with lingual forces exceeding facial forces. Multi-layer materials exhibited lower force magnitudes compared to single-layer materials. After ageing, a significant reduction in force was observed, with some materials experiencing up to a 50% decrease. Notably, multi-layer materials, especially Zendura VIVA, exhibited lower force decay. The force generated by aligners is influenced by both the aligner material and the direction of movement. Multi-layer materials exhibit superior performance compared to single-layer materials, primarily because of their lower initial force, which enhances patient comfort, and their capability to maintain consistent force application even after undergoing ageing.