The invention provides a preparation device and a method for an environmentally-friendly composite membrane with preferential alcohol permeability performance, and belongs to the membrane separation technology field. The preparation device comprises an air compressor, a filtration pressure-reducing valve, a triple valve, an atomizing nozzle, a solenoid valve, a loading tray, a baking lamp, a PLC controller, a low speed motor and a diaphragm pump. The solenoid valve control opening and closing of the atomizing nozzle. Polymers with a low viscosity are assembled on a basic membrane surface directly through pressure spraying in a solvent-free state, and furthermore, cross-linking agents and catalysts are sprayed in environmentally-friendly solvents, and therefore a composite separation membrane with a preferential alcohol permeability performance. The technology is simple and the composite membrane is environmentally friendly.