The invention relates to a method for simultaneous preparation of styrene and arylamine through a coupled reaction of side-chain alkylation and transfer hydrogenation. According to the method, preparation of styrene and an arylnitro compound through side-chain alkylation of toluene and methanol and preparation of arylamine through selective transfer hydrogenation of methanol are carried out in a same reaction system at the same time; methanol is used as a raw reaction material; side-chain alkylation and transfer hydrogenation are coupled with and promote each other during reaction process; and styrene and arylamine can be obtained in target products eventually. Since the method employed a coupled reaction of side-chain alkylation of toluene and methanol and transfer hydrogenation of a nitrobenzene substance, the conversion rate of toluene in a side-chain alkylation system is increased, the by-reaction of the target product styrene is reduced, the nitrobenzene substance and the transfer hydrogenation product arylamine are obtained, and the production efficiency of arylamine is improved.