The Letter presents a generalization of the kinetic model for radiative flows of reacting gas mixtures with strong vibrational and chemical non-equilibrium. The new model takes into account the vibration-electronic (VE) transitions and radiative transitions from the electronically excited states. A closed set of macroscopic equations taking into account the coupling of vibrational relaxation, chemical reactions and radiative transitions is derived. The peculiarities of non-equilibrium kinetics of CO in different conditions are discussed.