Dimethyl ether is a potential clean fuel and intermediate for other chemical synthesis, such as gasoline, ethylene, and acetic acid. To synthesize dimethyl ether from the traditional syngas process is an energy consuming process. More than one fourth of natural gas must be burned to generate heat for the steam reformation of natural gas. Here, we show a non-syngas process to synthesize dimethyl ether. This process consists of the conversion of methane to bromomethane by reacting methane with hydrogen bromide and oxygen and the hydrolysis of bromomethane to dimethyl ether. Through this process, methane can be high efficiently converted to dimethyl ether.