Monodispersed CoZr4(PO4)(6) microspheres with a diameter of 40 mu m were achieved via a combining solvothermal and calcination route. The crystallinity of the calcined microspheres with shell structure was improved, while the monodisperse property and morphologies remained. The possible formation mechanism of the porous CoZr4(PO4)(6) microspheres with nanoshell was proposed. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). Fourier transform infrared spectra (FT-IR) technologies, thermal analysis (TG and DSC), nitrogen adsorption-desorption isotherms and network analyzer. The sample calcined at 900 degrees C shows a strongest absorbability in the radar-wave absorbability test. (C) 2012 Elsevier Ltd. All rights reserved.