CdS/HgS/CdS nanoparticles consist of a CdS core, epitaxially covered by one or two monolayers of HgS and additional cladding layers of CdS. The present paper describes our efforts to identify the influence of CdS/HgS/CdS interfaces on the localization of the photogenerated carriers deduced from the magneto-optical properties of the materials. These were investigated by the utilization of optically detected magnetic resonance (ODMR) and double-beam photoluminescence spectroscopy. A photoluminescence (PL) spectrum of the studied material, consists of a dominant exciton located at the HgS layer, and additional non-excitonic band, presumably corresponding to the recombination of trapped carriers at the interface. The latter band can be attenuated using an additional red excitation. The ODMR measurements show the existence of two kinds of electron-hole recombination. These electron-hole pairs maybe trapped either at a twin packing of a CdS/HgS interface, or at an edge dislocation of an epitaxial HgS or a CdS cladding layer.