MFI-type gallosilicalite and galloaluminosilicate were synthesized by hydro-thermal method. For all the as-synthesized Ga-containing samples, Ga-71 MAS NMR spectra confirmed that the Ga3+ cations are located in the zeolite framework. As for the case in galloaluminosilicate, Ga3+ and Al3+ cations can enter the zeolitic site at the same time, but there is a competition between the two cations to incorporate into the zeolite framework. Quantitative MAS NMR results suggest that the incorporation of the Ga3+ cations is seriously inhibited by that of the Al3+ cations if they existed together, while the reversed process is not observed. The catalytic performances of non-oxidative aromatization of methane on these zeolite catalysts, with or without loading of MoO3, have been investigated. The results show that zeolites containing framework Ga species, which are excellent catalysts for propane aromatization, are poor catalyst supports for methane dehydro-aromatization. The catalytic performance of the molybdenum-loaded H-gallosilicate (MFI) catalysts present an activity for methane activation and subsequent aromatization. however, it is not as good as that of the Mo-loaded H-galloaluminosilicate (MFI) catalysts. Bearing this in mind, it was suggested that zeolitic acidity that originated from the heteroatom substitution is essential for catalyzing methane aromatization. The weaker acidity of framework GaO4-tetrahedral species as compared to framework AlO4- tetrahedral species is suggested to be responsible for the inferior activity for methane aromatization reaction.