Mo/HZSM-5 catalysts show good catalytic reactivity in the absence of oxygen for the dehydrogenation and aromatization of methane at 973 K. The active Mo species were investigated by combining catalytic studies on Mo/HZSM-5 catalysts before and after NH4OH extraction with XRD, BET, NH3-TPD and TPR analysis. The XRD patterns show that Mo species are well dispersed on the zeolite surface. The specific surface areas decrease with increasing Mo loading but they can be restored to a large extent by NH4OH extraction. NH3-TPD results suggest that the Mo species prefer to deposit on the strong acid sites of HZSM-5 zeolite. TPR profiles show that there is a kind of Mo species which is easily reduced. No TPR peaks could be obviously observed if the Mol HZSM-5 catalysts were extracted by NH4OH solution. The results of NH4OH extraction experiment and other relevant characterization studies suggest that there are several kinds of Mo species deposited on the surface. By referring to the Mo species on Al2O3 supported MoO3 samples, we propose that the dissolvable Mo species in NH4OH solution are MoO3 crystallites and their aggregates in octahedral coordination, while the unsoluble Mo species mainly are Al-2(MoO4)(3) and MoO42- in tetrahedrally coordinated form. The catalytic performance of Mo/HZSM-5 catalysts before and after NH4OH extraction illustrates that Mo species in small MoO3 crystallites with octahedral coordination form are active for methane activation in the absence of oxygen on Mo/HZSM-5 catalysts, while Mo species in tetrahedrally coordinated form is less active for the reaction.