In this work, a method composed of electrospinning technique and subsequent calcinations was used to fabricate Zn-Mn-O heterostructures with unique morphologies and microspheres composed of ZnO micro/nanofibers successfully. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were applied to characterize the morphology and the crystallinity of the samples. The mechanism was proposed based on the formation process of ZnO materials calcined under different temperatures. The photocatalytic activity of all the Zn-Mn-O heterostructures was systematically investigated in decomposing Methylene Blue (MB) under UV lamp irradiation. In addition, the magnetic properties of Zn-Mn-O heterostructures were evaluated by vibrating sample magnetometer (VSM), and it was observed that all the Zn-Mn-O heterostructures exhibit slight ferromagnetic properties which will contribute to the recycle of the catalysts. (c) 2011 Elsevier B.V. All rights reserved.