The reaction pathway and kinetics of CuGaSe 2 formation were investigated by monitoring the phase evolution of temperature ramp annealed or isothermally soaked bilayer glass/GaSe/CuSe precursor film using time-resolved, in situ high-temperature X-ray diffraction. Bilayer GaSe/CuSe precursor films were deposited on alkali-free thin glass substrates in a migration-enhanced epitaxial deposition system. The initial CuSe phase begins to transform to β-Cu 2− x Se at around 230 °C, followed by CuGaSe 2 formation accompanied by a decrease in the β-Cu 2− x Se peak intensity at around 260 °C. Both the parabolic and Avrami diffusion-controlled reaction models represented the experimental data very well over the entire temperature range (280–370 °C) of the set of isothermal experiments with estimated activation energies of 115(±16) and 124(±19) kJ/mol, respectively. Transmission electron microscopy–energy-dispersive X-ray spectrometry (TEM–EDS) analysis suggests that CuGaSe 2 forms at the interface of the initial GaSe and CuSe layers.