The gas-phase reactions of [TiAlO4]+ with methane have been explored by using FT-ICR mass spectrometry complemented by quantum chemical calculations. Interestingly, the [TiAlO4]+ ions can activate two methane molecules continuously. Moreover, in contrast to the previous reports on gas-phase methane activation by metal oxide clusters, in which hydrogen-atom transfer and/or proton-coupled electron transfer prevail, a hydride transfer process dominates the [TiAlO4]+/CH4 system. The associated electronic origins have been discussed, and such a terminal metal-oxo active center as addressed in the [TiAlO4]+ cluster has proven to be promising in the construction of efficient catalysts concerning methane conversion.