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Non-oxidative ethane dehydroaromatization to form aromatic hydrocarbons was investigated over Co supported on H-ZSM-5 catalysts prepared by two methods. Co/H-ZSM-5 prepared by an ion-exchange (IE) method exhibited high catalytic performance than Co/H-ZSM-5 prepared by an impregnation method thanks to low carbon deposition. Temperature programmed reduction measurements and X-ray absorption near edge structure analysis (XANES) indicate that only Co2+ cations exist at ion-exchange sites in Co/HZSM-5 prepared by the IE method. Therefore, Co2+ cations would activate ethane with less carbon deposition.