Abstract: A process for producing trichlorosilane by reacting silicon with hydrogen chloride, which comprises bringing at least one silane compound selected from the group consisting of dichlorosilane, monochlorosilane and monosilane into contact with silicon during or prior to a reaction between silicon and hydrogen chloride to remove silicon oxide on the surface of silicon, thereby improving the reactivity of silicon with hydrogen chloride to produce silicon trichloride stably. Further, an alkali metal compound is co-present in the reaction between silicon and hydrogen chloride to suppress the production of silicon tetrachloride, thereby making it possible to produce trichlorosilane at a high selectivity.