Heteropolyacids (HPAs) supported on the activated carbon (SiW12/C and PW1JC) have been used to study the formation of methyl tert-butyl ether (MTBE).Compared to the conventional commercial catalysts, Amberlyst-15 resin and HZSM-5, HPAs supported catalysts have been proved to have much higher catalytic activity under lower temperature, especially selectivity to MTBE is up to 100%. It may be due to the high acid strength of HPAs as well as the specialty of heteropolyanion.