The crystallization kinetics of Ge–Sb–Se chalcogenide glasses prepared by melt-quenching method was investigated using differential scanning calorimetry under non-isothermal conditions with several different heating rates. Kissinger's equation and Matusita model were employed to analyze kinetic crystallization behavior of the glasses. The crystallization parameters were calculated and the crystallization mechanism was studied. The results indicate that the crystallization activation energy increases rapidly at the glass with a mean coordination number (MCN) of 2.4, and reaches its maximum at MCN of 2.65. These two transition thresholds correspond to the structural phase transition in the glassy network. The evolution of the glass transition temperature (Tg), activation energy for crystallization (Ec), glass forming ability and thermal ability as functions of MCN and chemical composition might have substantial implication on screening the best glass for the application in photonics.