The purpose of the in vitro study is to investigate and compare the morphological features and the chemical stability in weight of two different polyurethane-based blends, Smart Track (LD30) and Exceed30 (EX30), used for orthodontic aligners manufacture before and after the oral usage. Twenty orthodontic aligners were randomly selected: 10 LD30 and 10 EX30, each group was divided in two subgroups, never used and intra-orally aged. By the employment of a Stereomicroscope, a section of 5 × 5 mm was cut from the buccal surface of the incisal region of each aligner. All samples were subjected to Scanning Electron Microscopy and Ageing tests in different solutions to simulate the hostility of the oral environment. The statistical method used was t-test. At SEM images, LD30 appears more homogeneous in texture respect to EX30. However, after clinical usage, both materials show significant structural alterations: findings have been supported by higher magnifications at SEM, by which it is clearly to observe many superficial cracks cross through the polymer structures of LD30U, absent in never used samples. LD30U surface becomes also smoother due to the disappearance of most of the conglomerates, but at the same time also rougher while EX30U shows a greater irregularity and porosity in which large and deep cracks are also highlighted. Although these changes occur persistently, in the aging tests no significant weight loss from both materials has been found, confirming the initial hypothesis of a good chemical stability and safety of both polyurethane mixtures even in conditions of severe hostility. LD30 is the expression of the …