Multi-colour emitting doped ZnS nanocrystals surface capped with pyridine (P-ZnS) or polyvinyl pyrrolidone (PVP-ZnS) have been synthesized by wet chemical methods. The photoluminescence studies show that the dopant related emission from P-ZnS nanocrystals are caused by the energy transfer from band-to-band excitation of the host lattice. However, in the case of PVP capped ZnS, considerable enhancement in the emission intensity was observed and the corresponding excitation spectra appeared dramatically broadened due to the presence of multiple excitation bands with peak maxima at 235, 253, 260, 275, and 310 nm. The bands from 235 to 275 nm are assigned to the electronic transitions in the chemisorbed PVP molecules whereas the excitation maximum around 310 nm corresponds to the band-to-band transition within the nanocrystalline ZnS host. The presence of PVP related energy bands in the excitation spectrum indicates the process of energy transfer from the surface adsorbed PVP molecules to dopant centers in ZnS nanocrystals. This study brings out a heterogeneous sensitizer-activator relation between organic surface adsorbate and doped semiconducting nanocrystals. © 2003 Elsevier Ltd. All rights reserved.