Hydrogenation of alkenes is one of the most fundamental transformations in organic synthesis, and widely used in the petrochemical, pharmaceutical, and food industries. Although numerous hydrogenation methods have been developed, novel types of catalysis with new mechanisms and new hydrogen sources are still desirable. Thioxanthone (TX) is widely used in energy‐transfer photoreactions, but rarely in photoredox processes. Herein we show that a catalytic amount of TfOH as a co‐catalyst can tune the properties of TX to make it a photoredox catalyst with highly enhanced oxidative capability in the hydrogenation of carbonylated alkenes with the cheap petroleum industrial product p‐xylene serving as the hydrogen source. Deuterium can also be introduced by this method by using D2O as the D source. To the best of our knowledge, this is the first example of using p‐xylene as a hydrogen source.