Energy transfer between highly vibrationally excited CO molecules and low-energy electrons is studied using kinetic modeling. The results are compared with those of experimental measurements in optically pumped CO. The effect of vibrational energy transfer by electrons from the high towards the low vibrational levels of CO, previously observed in the experiments, is reproduced in calculations. The best agreement with the experiment is obtained for an electron concentration in the plasma of n e = 2 × 10 11 cm −3 , which is consistent with the previous measurements of the vibrationally stimulated ionization rate. The results of kinetic modelling calculations provide better insight into the kinetics of energy exchange between vibrationally excited molecules and electrons.