The Co–B alloy can be prepared facilely by a solid-solid reaction of CoCl2•6H2O and KBH4 powders at room temperature. Various characterizations, such as the chemical analysis, inductively coupled plasma-atomic emission spectroscopy (ICP), powder X-ray diffraction, electron diffraction and TEM have been performed. The results indicate that the Co-B alloy obtained by the solid-solid reaction is amorphous nanoparticles. The composition of the alloy is Co1.36B. The average diameter of the Co–B alloy nanoparticles is 30nm–50nm. The room temperature solid-solid reaction is mainly a surface reaction. The direct solid solid reaction between the borohydride and some metal-salts is thermodynamically possible. This simple preparation method may also be used for the large-scale production of the amorphous nanoparticles of some metal-boron alloys.