The invention discloses a catalytic system for efficiently catalyzing indole silanization and proton transfer hydrogenation, and belongs to the technical field of organic synthesis. According to the catalytic system, indole and silane serve as raw materials, tris(pentafluorophenyl) boron (B (C6F5)3) serves as a catalyst, reaction is performed for 10 minutes at the indoor temperature to simultaneously achieve 3-position selective indole silanization and proton transfer hydrogenation or reaction is performed for 10-1440 minutes at the temperature ranging from 100 DEG C to 140 DEG C to achieve 3-position efficient and specific catalytic indole silanization. The catalytic system has the advantages that the catalytic system is convenient to operate, mild in reaction condition, rapid in reaction, high in conversion rate, less in catalyst consumption and applicable to various solvent systems or body systems without any solvents, raw materials are easily acquired, precious metal is omitted, a catalytic intermediate is high in stability and the like.