The invention discloses a preparation method of a CF2O-containing compound, and an intermediate compound and a preparation method thereof. The preparation method of a CF2O-containing compound, provided by the invention, comprises the following step: in solvent, in the presence of a catalyst, performing coupling reaction on 5-(bromo-difluoro-methoxy)-1,2,3-trifluorobenzene shown as Formula 1 and a Grignard reagent 3,5-difluoro-4'-propylbiphenyl-4-magnesium bromide shown as Formula 2, thus obtaining 4-(4-n-propyl)phenyl-3,5-difluoro-1',1'-difluorobenzyl-3,4,5-trifluorophenyl ether shown as Formula 3. The preparation method provided by the invention is simple to operate, mild in reaction conditions, convenient in posttreatment steps, high in reaction conversion rate, high in atom economy, friendly to environment, favorable in product purity and suitable for industrial production.