© 2016 American Chemical Society. Constant-temperature ab initio molecular dynamics is used to study reactions between molten LiI and gas phase molecules (O2, H2O, and I2) in an attempt to elucidate some aspects of the alkane oxidative dehydrogenation activity performed in the presence of molten LiI. We investigate the energy of reactions that produce LiIO, LiIO3, LiIO4, Li2O2, Li2O, LiOH, and I2. We find that the most favorable process is the formation of gaseous I2, coproduced with LiOH or Li2O (depending on the availability of water). If water is absent, then some LiIO4 will also be formed. However, this is unlikely to happen during oxidative dehydrogenation, because LiI is very hydroscopic and the oxidative dehydrogenation reaction produces water.