The search for novel photocatalysts that make use of almost the entire solar spectrum remains an ongoing task to achieve high efficiency in energy conversion. While titanium chalcogenides offer a variety of phase compositions with different photophysical properties, their photocatalytic performance in pollutant degradation has not been investigated to date. In contrast to the model photocatalyst titanium dioxide, titanium chalcogenides possess small band gaps which make them eligible to absorb light in the visible range up to the near-infrared region, thus making them interesting candidates for photocatalysis. Herein titanium chalcogenide-based photocatalysts are synthesized by the chemical vapor transport (CVT) method and studied for their photocatalytic activity towards pollutant degradation. A series of titanium chalcogenides TiXn (X = S, n = 1–3; X = Se, n = 2; X = Te, n = 1) have been characterized by a variety of physico-chemical methods. Due to the expected non-stoichiometry of some titanium sulfides, they offer a large number of defect states which make them interesting candidates for photocatalysis. Thus, these titanium-chalcogenides were systematically studied for the photocatalytic degradation of pollutants using methyl orange dye as the test pollutant under simulated sunlight. Particularly TiS and TiS3 show high photocatalytic and thermocatalytic activity, outperforming the activity of titanium dioxide (pure anatase). By controlling the ratios of titanium and chalcogen elements and the specific reaction conditions, a variety of titanium chalcogenides with different compositions and phases showing a high photocatalytic activity can be accessed. Furthermore, it is found that the formation of a titanium dioxide passivation layer during photocatalysis results in a titanium oxide/titanium sulfide heterostructure. This allows further enhancement of the photocatalytic and thermocatalytic activity compared to the bare Ti-chalcogenides.