Well-dispersed ZnAl2O4 spinel nanoparticles with an average crystalline size of 25.7 nm were synthesized successfully and easily by polymer-network and matrix-isolation-assisted calcination. The product microstructure and features were investigated by X-ray diffractometry, thermogravimetric and differential thermal analysis, Fourier transform-infrared spectroscopy, N-2 adsorption-desorption isotherms, and energy dispersive X-ray spectra. The morphology and optical performance of the asprepared ZnAl2O4 nanoparticles were characterized by scanning electron microscope, transmission electron microscopy, and photoluminescence spectrometer. Experimental results indicate that excess ZnO acted as the isolation medium is effective in preventing the sintering and agglomeration of ZnAl2O4 nanoparticles, and it also prevents their contamination. Then, high purity and well-dispersed ZnAl2O4 nanoparticles with single-crystal structure were obtained. (C) 2014 Elsevier Ltd. All rights reserved.