Oxidative dehydrogenation of propane with carbon dioxide (ODPC) has gained attention as a sustainable process capable of simultaneously producing propylene and reducing carbon dioxide (CO2) emissions. In this study, we developed a kinetic model of the ODPC over a silica-supported chromium oxide catalyst based on the Mars–van Krevelen (MvK) mechanism using the experimental data obtained under controlled conditions. The constructed model estimated both reactant conversions and propylene yield within an absolute error of 3% of the experimental data, confirming the integrity of the kinetic model. The kinetic analysis provides insight into the activation of propane and CO2 via several reactions occurring under ODPC conditions, emphasizing that the ODPC cycle is limited by the high energy barrier for CO2 activation. In addition, it allows comparison of the contributions of non-oxidative and oxidative dehydrogenation reactions, the two main reactions producing propylene under ODPC conditions. The estimation results show a significant increase in the reaction rate of ODPC with increasing CO2 partial pressure, in contrast to a nearly constant reaction rate of non-oxidative dehydrogenation, highlighting the promoting effect of CO2 in enhancing the ODPC reaction. Furthermore, the potential of the ODPC process is assessed by considering propylene productivity, net CO2 emissions, including the energy consumption for the separation process, and the global warming index of the energy grid. A comprehensive investigation of the ODPC process through controlled experiments, kinetic modeling and evaluation of net CO2 utilization provides insight into future strategies for using the ODPC as an efficient and eco-friendly process.