Carbon dioxide has been highlighted in recent years as a promising mild oxidant in the oxidative dehydrogenation (ODH) of low molecular weight alkanes over different metal oxide-based catalysts. Using CO2 as an alternative oxidizing agent has been shown to effectively suppress the undesirable combustion of the alkane under ODH conditions. In addition, its potential benefit for in-situ removal of carbon deposits via the reverse Boudouard reaction has been also underscored in the open literature. While oxygen assisted ODH involves a Mars van Krevelen mechanism, in ODH with CO2 it is shown that usually, olefin formation occurs mainly through a tandem scheme where direct alkane dehydrogenation is coupled with the reverse water gas shift (RWGS) reaction. However, the role of CO2 on the mechanism for the formation of olefins is still in question as different reaction pathways involving CO2 participation over supported metal oxide catalysts may occur. Since these pathways affect catalyst reactivity, we will discuss a combined approach where vibrational spectroscopy is coupled with catalytic measurements to provide insights into the role of CO2 on metal oxide stability.