The present work aims to study the formation of electroless Ni-B deposits and evaluation of their characteristic properties. An alkaline bath having nickel chloride as the source of nickel and borohydride as the reducing agent was used to prepare the electroless Ni-B deposits. The influence of variation in bath constituents as well as operating conditions on the plating rate, and, the nickel and boron content, of the resultant Ni-B deposits were studied. Selected deposits were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), evolved gas analysis (EGA), vibrating sample magnetometer (VSM) and transmission electron microscope (TEM), respectively, for assessing the phase content, phase transformation behaviour, liberation of hydrogen during crystallization, saturation magnetic moment and micro-structural features. The corrosion resistance of Ni-B deposits, in 3.5% sodium chloride solution, both in as-plated and heat-treated (450°C/1 h) conditions, was also evaluated by potentiostatic polarization and electrochemical impedance studies. XRD patterns reveal that Ni-B deposits of the present study are amorphous in as-plated condition and undergo phase transformation to crystalline nickel and nickel borides upon heat-treatment. DSC traces exhibit two exothermic peaks at 306 and 427°C, corresponding to the phase transformation of amorphous Ni-B to crystalline nickel and Ni 3B phases and the transformation of a higher phase compound to Ni3B and Ni2B, respectively. TEM microstructures and EGA strongly support the occurrence of phase transitions at 306 and 427°C. Electroless Ni-B deposits demonstrate a moderate corrosion resistance in 3.5% sodium chloride solution. The extent of corrosion resistance offered by electroless Ni-B deposits is relatively less compared to electroless Ni-9 wt.% P deposit. © 2003 Elsevier B.V. All rights reserved.