An RF-diplexed laser absorption technique is employed to resolve spectral transitions of CO 2 in the mid-infrared at MHz rates to infer non-equilibrium temperatures of rotation and vibration. A distributed feedback interband cascade laser (DFB-ICL) resolves 7 transitions within the CO 2 fundamental asymmetric stretch band near 4.19 µm, representing a range of rotational and vibrational energies. Non-equilibrium spectra are resolved at MHz rates and fit with a two-temperature model for line intensities. The sensor is demonstrated on a high enthalpy shock tube, targeting temperatures between 1250 -3500 K and sub-atmospheric pressures in various CO 2 -Ar gas mixtures. Tests have shown that this sensor provides sensitive temperature measurements with 1-µs resolution over a wide range of conditions relevant to Mars entry radiation. Vibrational relaxation times on the order of 10 µs are resolved and compared to existing models.