Heterostructures consisting of tungsten disulfide (WS2) and cadmium sulfide (CdS) have shown longer emission decay life time and significantly quenched fluorescence emission in comparison to pure materials (WS2 and CdS). CdS@WS2 heterostructures also show a significant enhancement in light absorption across the entire visible spectrum with a change in the slope of the absorption edge pertaining to WS2 nanostructures in the heterostructures. This leads to higher number of charge carriers, improved charge separation as well as charge migration from the material surface to the back contact. In photoelectrochemical water splitting, the heterostructures exhibited a twentyfold increase in photocurrent density (0.15 mA cm-2) at 1.23 V vs. RHE in comparison to pristine sulfides. The heterostructures also showed a good reduction ratio of >83% in 120 minutes [Cr(vi) to Cr(iii)] in a mixture of Cr(vi)/Ni(ii) ions and RhB. Hence, CdS@WS2 heterostructures with improved charge carrier dynamics can find several applications as photocatalysts. © 2020 The Royal Society of Chemistry.