Nanoparticles of iron boride (Fe2B, Fe2B coated in SiO2, FexCo2−xB coated in SiO2) were synthesized using the reduction of metal ions by sodium borohydride. X-ray diffraction confirms the amorphicity of the coated compounds and scanning electron microscope imaging revealed the nanoparticulated structure of all compounds. The splitting between zero-field-cooled and field-cooled temperature dependent magnetization curves point to the blocking of superparamagnetic particles magnetization. Magnetic hysteresis loops are however consistent with the combined effects of blocked superparamagnetic and ferromagnetic (multidomain) particles. The observed quite complex magnetic behaviour is in accordance with structural studies, where additional phases and broad distribution of particle sizes were identified.