The invention discloses a polystyrene/polystyrene anion exchange alloy film preparation method, which comprises the following steps: adding a polymerized monomer solution which is composed of 1-(chloromethyl)-4-ethenylbenzene, a cross-linking agent and an initiator into a polyvinylidene fluoride solution, and then heating for copolymerization, extruding, solidifying, granulating, drying, crushing and other steps for obtaining PCMS/polyvinylidene fluoride alloy powder; reacting the alloy powder and the amination solution, washing, transforming, drying and obtaining the anion exchange powder; finally using a hot pressing moulding method, adding auxiliary material, banburying, milling, pulling sheet, hot pressing and obtaining polyvinylidene fluoride/ polystyrene anion exchange alloy membrane. The anion exchange alloy membrane manufactured by the invention has the advantages of high-molecular interpenetrating network structure, whose membrane area resistance is greatly lower than the traditional interphase anion exchange membrane, and the comprehensive properties of the membrane approaches to the homogeneous anion exchange membrane. The invention avoids the usage of carcinogenic reagent chloromethyl ether, and is easy for realization of industrial production.