We use a zero-dimensional reaction kinetics model to simulate CO2 conversion in microwave discharges where the excitation of the vibrational levels plays a significant role in the dissociation kinetics. The model includes a description of the CO2 vibrational kinetics, taking into account state-specific VT and VV relaxation reactions and the effect of vibrational excitation on other chemical reactions. The model is used to simulate a general tubular microwave reactor, where a stream of CO2 flows through a plasma column generated by microwave radiation. We study the effects of the internal plasma parameters, namely the reduced electric field, electron density and the total specific energy input, on the CO2 conversion and its energy efficiency. We report the highest energy efficiency (up to 30%) for a specific energy input in the range 0.4–1.0 eV/molecule and a reduced electric field in the range 50–100 Td and for high values of the electron density (an ionization degree greater than 10−5). The energy efficiency is mainly limited by the VT relaxation which contributes dominantly to the vibrational energy losses and also contributes significantly to the heating of the reacting gas. The model analysis provides useful insight into the potential and limitations of CO2 conversion in microwave discharges.