A microscopic theory of the appearance of electron-phonon instability and a semiconductor-metal phase transition away from thermodynamic equilibrium in a Peierls system upon the optical excitation of electron-hole pairs is devised. An equation which specifies the dependence of the order parameter of the phase transition and the uniquely related gap width in the electron spectrum, on the concentration n of conduction-band electrons is obtained. The critical concentration n=nc, above which the semiconductor phase of the system is unstable toward the transition to the metallic state, is calculated. A comparison with an experiment on the irradiation of a substrate-supported vanadium dioxide film by a laser pulse is made.