Thermal transformations of potassium-exchanged zeolite A and the X-ray amorphous material obtained by ball milling the potassium-exchanged zeolite A were investigated by different methods, such as differential thermogravimetric analysis (DTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Controlled heating of crystalline, potassium-exchanged zeolite A causes a phase transformation in the sequence : [0.22 Na2O, 0.78 K2O]. Al2O3 . 2SiO(2) . 3.48 H2O double right arrow amorphous double right arrow kalsilite + kaliophilite, while the heating of mechanochemically amorphous potassium-exchanged zeolite A results in its transformation into a mixture of kalsilite and kaliophilite. The differences in the pathways of the transformation processes are discussed in terms of the structural properties of the starting materials.