The vibrational levels of KH(X1Σ+, v″=0–3) were generated in the reaction of K (5P) and H2. Vibrational state total relaxation rate coefficients k v ″ ( CO 2 ) for KH (v″=14–21) are measured in an overtone pump-probe configuration. The rate coefficient k v ″ ( CO 2 ) is strongly dependent on vibrational quantum number. Scattered CO2 (0000, 32≤J≤48) molecules were excited to CO2 (1005, J+1) states. The rotational temperatures of CO2 (0000, J=32–48) states populated by collisions with highly vibrationally excited KH (v″=14–21) are obtained. The average rotational energy of the scattered CO2 molecules is increased by a factor of 2.33 when KH level v″=14 increases to v″=21. The average translational energy of the scattered CO2 molecules is increased roughly linearly as a function of CO2 J state. Under single collision conditions, state-specific energy transfer rate coefficients for collisions of highly excited KH with CO2 are obtained. For v″=19, the integrated rate coefficients kint increases by a factor of 4.5 to v″=14.