Metal borides have long-standing uses due to their desirable chemical and physical properties such as high melting points, hardness, electrical conductivity, and chemical stability. Typical metal boride preparations utilize high-energy and/or slow thermal heating processes. This report details a facile, solvent-free single-step synthesis of several crystalline metal monoborides containing earth-abundant transition metals. Rapid and exothermic self-propagating solid-state metathesis (SSM) reactions between metal halides and MgB 2 form crystalline FeB, CoB, and NiB in seconds without sustained external heating and with high isolated product yields (∼80%). The metal borides are formed using a well-studied MgB 2 precursor and compared to reactions using separate Mg and B reactants, which also produce self-propagating reactions and form crystalline metal borides. These SSM reactions are sufficiently exothermic to theoretically raise reaction temperatures to the boiling point of the MgCl 2 byproduct (1412 °C). The chemically robust monoborides were examined for their ability to perform electrocatalytic water oxidation and reduction. Crystalline CoB and NiB embedded on carbon wax electrodes exhibit moderate and stable bifunctional electrocatalytic water splitting activity, while FeB only shows appreciable hydrogen evolution activity. Analysis of catalyst particles after extended electrocatalytic experiments shows that the bulk crystalline metal borides remain intact during electrochemical water-splitting reactions though surface oxygen species may impact electrocatalytic activity.