Three-dimensional (3D) porous ZnO nanostructures were synthesized via one-pot solvothermal treatment. The structural, morphological and spectral properties were investigated using X-ray diffraction (XRD), N-2 sorption measurement field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Raman spectroscopy, and photoluminescence (PL) spectroscopy. It was found that the minimum reflection loss value of ZnO calcined at 500 degrees C reached -5.62 dB at 16.24 GHz with the thickness of 2.5 mm, which had a superior performance of microwave absorption than those uncalcined and calcined at 600 degrees C. The possible mechanism for the formation of porous ZnO hollow spheres was proposed. The relationship of the ZnO microstructure and the microwave absorption properties was revealed via studying the dielectric loss and interference multi-reflection absorption in this paper as well. In addition, the photoluminescence results show that the uncalcined ZnO and porous hollow ZnO calcined at 500 degrees C and 600 degrees C show a narrow and sharp UV emission at 355.8 nm and a relatively broad visible spectra emission at around 423 nm. (C) 2015 Elsevier B.V. All rights reserved.