Abstract In this study, ZnS coated ZnO nanorods were synthesized using a simple, cost effective two-step chemical method. A continuous coating of ZnS on a ZnO nanorod, having a uniform thickness, is demonstrated using high resolution transmission electron microscopy, electron energy loss spectroscopy and selected area diffraction (SAD). These core–shell structures can be produced at relatively low temperatures (75°C) and within relatively short times (3h). The ZnS coating exhibits a polycrystalline structure with a lattice parameter of 5.35Å, which is 1.1% smaller than the unstrained cubic zinc-blende structure. The SAD pattern taken at the ZnO–ZnS interface exhibits a partial epitaxial relationship, where (10–10) ZnO//(111) ZnS. Our detailed analysis shows that the ZnS shell comprises two different regions: a ZnS rich inner shell region is produced via the first sulphidation process, followed by a mixture of ZnO and ZnS in the outer shell region during the second treatment. From the detailed microscopy results a growth mechanism is proposed for each step of the sulphidation process. The results are complemented by room temperature photoluminescence spectroscopy. Strong emission from free excitons in ZnO is observed at 3.27eV before ZnS coating, while a composite band peaking at 2.9eV is measured after sulphidation. The origin of the latter will be discussed.