Industrial emissions of volatile organic compounds are urgently addressed for their toxicity and carcinogenicity to humans. Developing efficient and eco-friendly reforming technology of volatile organic compounds is important but still a great challenge. A promising strategy is to generate hydrogen-rich gas for solid oxide fuel cells by autothermal reforming of VOCs. In this study, we found a more desirable commercial catalyst (NiO/K2O-γ-Al2O3) for the autothermal reforming of VOCs. The performance of autothermal reforming of toluene as a model compound over a NiO/K2O-γ-Al2O3 catalyst fitted well with the simulation results at the optimum operating conditions calculated based on a simulation using Aspen PlusV11.0 software. Furthermore, the axial temperature distribution of the catalyst bed was monitored during the reaction, which demonstrated that the reaction system was self-sustaining. Eventually, actual volatile organic compounds from the chemical factory (C9, C10, toluene, paraxylene, diesel, benzene, kerosene, raffinate oil) were completely reformed over NiO/K2O-γ-Al2O3. Reducing emissions of VOCs and generating hydrogen-rich gas as a fuel from the autothermal reforming of VOCs is a promising strategy.