The formation of KrCl*, KrBr*, and KrF* exciplexes, in electron beam irradiated mixtures of krypton with either CF3Cl, CF3Br, SF6, or CF4, are observed to be formed by two distinct and kinetically resolvable time‐dependent processes. The rate of one process is total electron beam energy (dose per pulse) independent but dependent on the partial pressures of the halogen source. This process is attributed to a reaction between high electronic excited states of krypton and the halogen source. The second process is dependent on the total absorbed electron beam energy per pulse and is shown to be due to ion recombination processes. Specifically, the formation is due to a combination of krypton positive ions and halogen negative ions, the latter being formed by dissociative electron capture by the halogen source. This process produces KrF* in high vibrational levels.