Well-defined crystalline ZnSe microspheres have been fabricated successfully via a simple solvothermal route under mild conditions in the presence of ethylenediamine tetraacetic acid disodium salt (Na(2)EDTA) and octadecylamine (ODA). X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectrum (EDS), X-ray photoelectron spectra (XPS), Fourier transform-infrared spectroscopy (FT-IR), and photoluminescence spectra (PL) were used to characterize the phase structures, morphologies, and properties of the products. The result of XRD demonstrated that we obtained ZnSe products crystallized well with a stilleite structure. The influencing elements such as reaction time, sodium hydroxide (NaOH), addition of chelating reagent Na(2)EDTA, and the water/ethanol volume ratio were investigated, and the possible formation mechanism was also proposed. Furthermore, the experimental result indicated that ZnSe microspheres showed blue emission under ultraviolet excitation. (C) 2012 Elsevier Inc. All rights reserved.