The utilization of carbon dioxide (CO2) which is one of the main contributors to the greenhouse effect, has been a topic of global interest, from both fundamental and practical viewpoints. In addition to be the sources of carbon, CO2 might also be utilized as an oxygen source or oxidant, because it can be considered to be a nontraditional (mild) oxidant and oxygen transfer agent. In this paper, CO2 as an oxidant for the selective oxidative conversions of alkanes to alkenes has been reviewed, including methane coupling to ethylene, C-2-C-4 alkanes dehydrogenation to their corresponding olefins, dehydroaromerization of lower hydrocarbons to benzene, and dehydrogenation of ethylbenzene to styrene. It has been shown that CO2 has the potential to offer a promising alternative to oxygen for selective oxidation, whereas the catalyst development is the key to the applications.