In this paper, the thermal decomposition of crystalline Al(OH)3 was studied over the temperature range of 260–400 °C for particles with a size between 10 and 150 µm. The weight losses and thermal effects occurring in each of the dehydration process were assessed using thermogravimetry (TG) and differential scanning calorimetry (DSC) thermal analysis. X-ray diffraction (XRD) patterns, refined by the Rietveld method, were used for mineral phase identification, phase composition analysis, and crystallinity degree determination. Moreover, the particle size distributions and their corresponding D10, D50, and D90 numeric values were determined with a laser analyzer. We observed a strong relationship between the calcination temperature, the initial gibbsite grade particle size, and the crystallinity of the resulting powders. Hence, for all endothermic effects identified by DSC, the associated temperature values significantly decreased insofar as the particle dimensions decreased. When the gibbsite was calcined at a low temperature, we identified small amounts of boehmite phase along with amorphous new phases and unconverted gibbsite, while the powders calcined at 400 °C gradually yielded a mixture of boehmite and crystalized γ-Al2O3. The crystallinity % of all phase transition products declined with the increase in particle size or temperature for all the samples.