Titanium oxide is widely applied as a photocatalyst. However, its low efficiency and narrow light absorption range are two main disadvantages that severely impede its practical application. In this work, black TiOx films with different chemical compositions were fabricated by tuning target voltage and controlling O2 flow during reactive DC magnetron sputtering. The optimized TiOx films with mixed phases (TiO, Ti2O3, Ti3O5, and TiO2) exhibited fantastic photothermal and photocatalytic activity by combining high light-absorptive Ti2O3 and Ti3O5 phases with the photocatalytic TiO2 phase. The sample prepared with oxygen flow at 5.6 ± 0.2 sccm and target voltage near 400 V exhibited excellent optical absorbance of 89.29% under visible light, which could improve surface temperature to 114 °C under sunlight. This film could degrade Rhodamine-B up to 74% after 150 min of UV irradiation. In a word, this work provides a guideline for fabricating black TiOx films with photothermal-assisted photocatalytic activity by reactive DC magnetron sputtering, which could avoid the usage of hydrogen and is convenient for quantity preparation.