CeO2 microspheres, with an average diameter of 1 mu m, have been successfully prepared through a facile 1,4-dioxane-assisted solvothermal synthesis, where 1,4-dioxane is acted as a capping agent for the first time. By varying the solvent ratio, the formation mechanism for the CeO2 microspheres has been proposed on an isotropic growth through the capping function of 1,4-dioxane. The strong UV-vis spectra result indicates that the CeO2 microspheres are suitable as an UV blocking and shielding material. The cyclic voltammetric measurements of hemoglobin immobilized on CeO2-Nafion modified glassy carbon electrode reveal a typical characteristic of surface-controlled thin-layer electrochemical behavior of the CeO2 microspheres. (C) 2013 Elsevier Ltd. All rights reserved.