Crystallized FeB and Fe2B powders were synthesized by a molten salt method with elemental Fe and B powders as starting materials. The results indicated that the presence of molten NaCl/KCl salts and the excess of Fe or B powders were essential to obtain pure FeB or Fe2B powders. The formation mechanism of iron borides was investigated by examining the phase compositions of the obtained products with different molar ratio of Fe/B. It was found that Fe powders firstly reacted with B powders to form Fe2B phase, and FeB phase formed from the reaction between Fe2B and excessive B. The as-synthesized FeB and Fe2B powders had a uniform short-rod and plate like morphology, respectively. Both FeB and Fe2B exhibited typical soft magnetic behavior. The saturation magnetization and the coercivity were 36.4 emu/g and 15.5 kA/m for FeB, 126.9 emu/g and 6.1 kA/m for Fe2B, respectively. The electrochemical performances of the as-synthesized FeB powders were evaluated by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance test.