The significant role played by water in the mechanochemical synthesis of highly distorted aluminum hydroxide fluorides is on the main focus of this research paper. The importance of water in the synthesis was evaluated considering separately combinations of O/OH sources (Al(OH)(3), Al2O3) and fluorine sources with or without structural water (beta-AlF3.3H(2)O, alpha-AlF3). Each system was studied by typical bulk and surface characterization techniques (XRD, MAS NMR, DTA-TG, NH3-TPD) and compared to each other in order to gain a more comprehensive insight of the importance of including water in the synthesis of amorphous aluminum hydroxide fluorides.