In-situ High Temperature X-ray Diffraction (HTXRD) and Differential Scanning Calorimetric (DSC) studies were performed on a sol–gel derived binary compound of a calcia–alumina (C12A7) system consisting of calcium oxide (CaO) and aluminium oxide (Al 2 O 3 ) in a ratio of 12:7 for in situ investigation into the phase transformations under progressively increasing thermal activation from room-temperature to 1200°C. The crystallisation of amorphous samples formulated at room-temperature on magnesium oxide (MgO) single crystal (100) substrates was found to be complete on heat treatment at 1100°C for 3h. This observation was further supported by independent Fourier Transform Infrared (FTIR) and Raman Spectroscopies. Values of 348kJ/mol and 375kJ/mol were estimated from Kissinger plots for activation energies of crystallisation of CaO and Al 2 O 3 constituents, respectively.