Previous studies have shown that radiotherapy of the head and neck region can cause direct changes in dental structure. This study evaluated the effect of different solutions on the dentin chemical composition and collagen structure of irradiated dentin. Sixty maxillary canines were distributed in 2 groups (n=30): non-irradiated and irradiated (radiotherapy: X-rays of 6 MV in 30 cycles of 2 Gy to 60 Gy). The teeth were sectioned, sanded, and polished to obtain 3x3x2 mm fragments, which were redistributed in 3 subgroups (n=10) according to the treatment employed: chlorhexidine 2% (CL), chitosan 0.2% (QT), and 0.5 M carbodiimide (EDC). The samples were analyzed in FTIR at time zero (T0-control) and after 1 (T1), 3 (T3), and 5 (T5) minutes of immersion in the tested solutions. The data for the areas of the carbonate (C), amide I (AI) bands, and the ratio between the areas of the amide III/proline and hydroxyproline (AIII/PH) bands were analyzed using ANOVA and Tukey test (?=5%). QT showed lower C values at T1, T3, and T5 (P<0.0001), presenting lower values when compared to CL and EDC subgroups (P<0.05). AI values at T3 and T5 were higher than T0-control and T1, independently of the radiotherapy and dentin treatment factors (P<0.05). At T0-control, the AIII/PH ratio was lower in the irradiated group (P<0.05), whereas the EDC treatment at T1, T3, and T5 and QT at T3 and T5 increased these values (P<0.05), making them similar to non-irradiated subgroups (P>0.05). Radiotherapy changes the secondary structure of collagen, and EDC was able to restore collagen integrity after 1 minute of immersion, without changing dentin inorganic composition.