Titanium aluminum carbide exhibits a unique combination of characteristics of both metals and ceramics coupled with an unusual combination of mechanical, electrical and thermal properties. In this paper, the effect of high-vacuum annealing on the phase stability and phase transition of Ti3AlC2 at up to 1550°C was studied using in-situ neutron diffraction. The decomposition of Ti3AlC2 into TiC was observed from the change of relative phase abundances as a function of temperature. The apparent activation energies of phase decomposition was determined to be -71.9 kJ/mol. Near-surface composition depth profiling using grazingincidence synchrotron radiation diffraction has revealed a graded phase composition in vacuum-decomposed surfaces.