This article presents an experimental demonstration of a high-pressure unconditionally stable nonequilibrium molecular plasma sustained by a combination of a continuous wave CO laser and a sub-breakdown radio frequency (rf) electric field. The plasma is sustained in a CO/N2 mixture containing trace amounts of NO or O2 at pressures of P=0.4–1.2 atm. The initial ionization of the gases is produced by an associative ionization mechanism in collisions of two CO molecules excited to high vibrational levels by resonance absorption of the CO laser radiation with subsequent vibration-vibration (V-V) pumping. Further vibrational excitation of both CO and N2 is produced by free electrons heated by the applied rf field, which in turn produces additional ionization of these species by the associative ionization mechanism. In the present experiments, the reduced electric field, E/N, is sufficiently low to preclude field-induced electron impact ionization. Unconditional stability of the resultant cold molecular plasma is enabled by the negative feedback between gas heating and the associative ionization rate. Trace amounts of nitric oxide or oxygen added to the baseline CO/N2 gas mixture considerably reduce the electron–ion dissociative recombination rate and thereby significantly increase the initial electron density. This allows triggering of the rf power coupling to the vibrational energy modes of the gas mixture. Vibrational level populations of CO and N2 are monitored by infrared emission spectroscopy and spontaneous Raman spectroscopy. The experiments demonstrate that the use of a sub-- breakdown rf field in addition to the CO laser allows an increase of the plasma volume by about an order of magnitude. Also, CO infrared emission spectra show that with the rf voltage turned on the number of vibrationally excited CO molecules along the line of sight increase by a factor of 3–7. Finally, spontaneous Raman spectra of N2 show that with the rf voltage the vibrational temperature of nitrogen increases by up to 30%. This novel energy efficient approach allows sustaining large-volume high-pressure molecular plasmas without the use of a high-power CO laser. This opens a possibility of using the present technique for high-yield plasma chemical synthesis and plasma material processing. © 2001 American Institute of Physics.