Anhydrous carbamazepine (CBZ) is an anti-convulsant drug commonly used to treat epilepsy and relieve trigeminal neuralgia. The presence of the dihydrate form in commercial CBZ tablets can change the dissolution rate of the active pharmaceutical ingredient (API), thus decreasing its activity. The hydration transformation can occur during wet granulation or storage, within a few weeks, depending on the ambient conditions. This work aims to investigate the effect of relative humidity (RH) in the transition of pure anhydrous CBZ (CBZ III) into the hydrate form by using confocal Raman microscopy with cluster analysis (CA). Firstly, several tablets of pure CBZ III containing different amounts of CBZ DH (50%, 10%, 1%, 0.5%) were prepared and analyzed by Raman imaging with CA. Our results show that CBZ DH crystals can be detected in the CBZ III tablets, at as low a concentration as 0.5%, giving distinct Raman features for the analysed polymorphs. The stability of pure anhydrous (CBZ III) tablets was then monitored by Raman imaging at room temperature (20-22 °C) and different RH (6%, 60% and 89%). The Raman imaging with CA showed that the anhydrous CBZ tablets start to convert into the hydrate form after 48 h, and it completely changes after 120 hours (5 days) at RH 89%. The tablets exposed to RH 6% and 60% did not demonstrate the presence of CBZ DH after 1 week of exposure. The exposure time was extended for 9 months in the former, and no CBZ DH was observed. A comparative study using IR imaging was also performed, demonstrating the viability of these vibrational imaging techniques as valuable tools to monitor the hydration process of active pharmaceutical ingredients.