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Background: Relationships between reflectivity, hardness and chemical composition of the dispersed phase, included in orthodontic composites Transbond XTTM (Trans), Light-Cure Orthodontic Paste (Leone) and Bisco Ortho Bracket Paste LC (Bisco), were investigated in vitro to evaluate whether reflectivity results can be useful in internal material composition interpretation, thus obtaining information on mechanical behaviours. Methods: Light transmission through 36 resin discs was measured with a UV/Vis spectrophotometer, evaluating the spectral range from 190–1100 nm. To have a benchmark of material hardness and internal composition, Vickers measurements and Cross-Sectional Focus Ion Beam Scanning Electron Microscopy (FIB/SEM) analysis were provided. Results: Bisco has the highest reflectivity, Leone shows an absorption pattern in the UV region similar to Bisco and Transbond has the lowest reflectivity compared to the others. This trend is confirmed by FIB/SEM imaging, showing a more similar induced roughness and internal composition for Bisco and Leone, with respect to Transbond. Higher filler presence in the composition of Bisco and Leone justifies a higher hardness of these two materials, with respect to Transbond, as confirmed by Vickers measurements. Conclusions: Bisco and Leone show similar optical responses and similarities in mechanical performance. This statement is explained by the lower and similar filler content as confirmed also by FIB/SEM analysis. The inner composition of Bisco and Leone provides a higher value of microhardness, as demonstrated by Vickers measurements. Therefore, this study confirms that the UV-Vis analysis can also offer a significant overview on the internal material composition, thus indirectly providing information on the mechanical properties of orthodontic composites.