The invention provides a process method for preparing ethyl tert-butyl ether. The process method comprises the following steps of: taking isobutene and ethanol as raw materials, and using a heteropoly acid / titanium-based complex oxide catalyst to prepare the ethyl tert-butyl ether, wherein the heteropoly acid / titanium-based complex oxide catalyst takes a complex oxide as a carrier and takes heteropoly acid as an active component, the complex oxide is one or more of titanium-based complex oxides in TiO2-SiO2 or TiO2-ZrO2, and the heteropoly acid is one or more of phosphotungstic acid, silicotungstic acid, arsenotungstic acid, germanotungtic acid, phosphomolybdic acid, silicomolybdic acid, arsenomolybdic acid and germanomolybdic acid. According to the process method provided by the invention, the catalyst adopting the titanium-based complex oxide to load the heteropoly acid is adopted, so that the shortcomings of inactivation of the catalyst and reduced conversion rate, which are caused by easiness in damaging the Keggin structure of the heteropoly acid of the loaded heteropoly acid catalyst, easiness in loss of acid amount and difficulty in separation, can be overcome.