A by-product mixture produced in a process for producing polycrystalline silicon is made to react with chlorine to form tetrachlorosilane (STC) distillate in a chlorination reaction vessel, and the tetrachlorosilane (STC) distillate is made to react with hydrogen in a hydrogenation reaction vessel to be converted into trichlorosilane (TCS). In the chlorination step, methyl chlorosilanes having boiling points close to TCS are hyper-chlorinated to be converted into hyper-chlorinated methyl chlorosilanes having higher boiling points, which facilitates the hyper-chlorinated methyl chlorosilanes to be separated into high concentration, and inhibits carbon from contaminating the polycrystalline silicon. A donor/acceptor eliminator is provided in the circulation cycle for producing TCS, and accordingly there is no need to take out a by-product produced in the process for producing TCS to the outside of the system, which can highly purify the TCS.