The composites of Co-B coatings on hollow microspheres (Co-B/HMSs) have been successfully synthesized through electroless plating in this paper. The time-dependent microstructure evolution and magnetic properties of the composites were carefully investigated by scanning electron microscope (SEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometer (VSM). It was found that small Co-B clusters appeared on the surface of hollow microspheres at catalytic nuclei during the initial stage. Further growth, they converged to form continuous coatings, which were actually stacking of Co-B nuclei. Interestingly, there was an increment of B content in the coating as time wore on, this phenomenon could be interpreted by electrochemical mechanism. Besides, the composites showedmagnetic properties, which might be potentially important for the novel materials as magnetic carriers. (C) 2009 Elsevier B. V. All rights reserved.