Quantum chemical calculations using density functional theory (DFT) at the B3LYP level have been performed to investigate the mechanism of dehydrogenation of cyclohexane catalyzed by NiTi+. A complete exploration of the quartet and doublet potential energy surfaces (PESs) was displayed. The result showed that the entire reaction proceeded in mixed PESs. In the dehydrogenation of cyclohexane catalyzed by NiTi+, there are two competing channels: CH bond activation and CC bond activation. Since higher energy was required to activate the CC bond, only exclusive CH bond activation was observed. To further explore the bonding patterns of NiTi+, natural bond orbital (NBO) analysis was performed. In addition, the density of states (DOS) analysis of the initial complexes was carried out. The result for NiTi+ activated cyclohexane was thoroughly compared with those for Ti2+ and Ni2+, meanwhile also against available data.