A new route for the synthesis of methyl tert-butyl ether (MTBE) from isobutane using a single catalytic system has been developed. The key of the process is the use of a bifunctional material, Al-TS-1, capable of catalyzing the liquid-phase oxidation of isobutane with H2O2 and subsequently the etherification with methanol. The procedure carried out, simultaneously or sequentially, both reactions (oxidation and acid catalysis) as well as the influence of the reaction parameters has been studied. A two-stage process at two temperature levels was selected, according to the results obtained by studying both reactions separately. In addition, the influence of other reaction parameters, such as reactant molar ratios, solvent concentration, and catalyst composition, has been investigated to establish the optimum conditions to yield MTBE.