Mouthwashes are used during dental treatments to mitigate the complications caused by poor oral hygiene. However, these solutions also affect the properties of dental appliances, including those used in orthodontics. This point has been investigated in this study focusing on the changes in mechanical properties of polymeric orthodontic ligature ties. Commercial ties from four brands were characterized in terms of their maximum forces and displacement, delivery forces, molecular structures, and microscopic morphology. These properties were compared against the ties, which were rinsed with commercial mouthwashes from three manufacturers. The results showed that mouthwash rinsing significantly reduced the maximum bearable forces of ligature ties by up to 73.1%, whereas the reduction in their maximum displacement was up to 74.5% across all tested brands. Significant changes in microscopic morphology of ligature ties were observed after mouthwash rinsing, but not their molecular structure. Furthermore, mouthwash rinsing also reduced the delivery forces from ligature ties by between 20.9 and 32.9% at their first deformation cycle. It can be concluded from this study that mouthwashes have significant impact on the mechanical properties of polymeric orthodontic ligature ties and could also potentially affect the overall efficacy of orthodontic and other dental treatments.