Lindlar's catalyst, i. e., calcium carbonate‐supported palladium (Pd) modified with lead, has been used for semihydrogenation of an alkynyl group in the presence of hydrogen gas (H2). We examined hydrogenation of an alkynyl group in organosilane and hydrocarbon in methanolic suspensions of a Pd‐loaded titanium(IV) oxide (Pd−TiO2) photocatalyst without the use of additives and H2. In the photocatalytic reaction, Pd particles worked as co‐catalysts for hydrogenation and alkyne hydrogenation had priority to alkene hydrogenation. Since the Pd co‐catalyst was temporarily deactivated during the reaction owing to accumulation of the oxidized product(s) of methanol, the capacity of hydrogenation of the unsaturated C−C bond was limited. By optimizing the capacity and amount of alkynes, almost complete semihydrogenation of alkynes was achieved under a poison‐free condition. Pd−TiO2 can be regenerated by very simple treatments, i. e., washing and drying at room temperature.