Catalytic combustion has become a promising technology to address the accelerating volatile organic compounds (VOCs) emissions. In this work, cobalt modified ZSM-5 zeolite catalysts (3-18 wt % Co) were prepared to investigate the combustion of n-butane (one typical model component of VOCs). The performances of catalysts were evaluated by conducting experiments in a flow tube reactor. XRD, BET, FT-IR, and XPS were also utilized to characterize their physicochemical properties. A significant enhancement of the catalytic activity was demonstrated in terms of the cobalt supported over ZSM-5, with an optimal cobalt loading of 7 wt %. The excellent catalytic activity of 7 wt % Co-ZSM-5 is mainly attributed to a higher concentration of active surface Co3+ species. Furthermore, DFT calculations indicated that the role of Co can enhance the activity by decreasing the activation barriers for C-H bond cleavage. In addition, the primary reaction mechanism of n-butane combustion on Co-ZSM-5 was also revealed.