Metal phosphides from the 3d period exhibit a range of structures and compositions. Many metal-rich phosphides and monophosphides function as heterogeneous electrocatalysts in the hydrogen evolution reaction. This paper describes the direct and tin flux-assisted synthesis of phosphorus-rich metal phosphides with MP2 or MP3 compositions. The facile synthesis of FeP2, CoP3, NiP2, and CuP2 is thermochemically driven by PCl3 formation from reactions of anhydrous metal halides and P-4 vapor at 500 degrees C. Well-crystallized micrometer-sized particles result from these solvent-free reactions. A tin flux leads to more complete reactions at lower temperature for FeP2 and enables synthesis of a monoclinic polymorph of NiP2 rather than the kinetic cubic product formed by direct reaction. These crystalline metal phosphides are investigated as electrocatalyts for hydrogen evolution in acidic and buffered aqueous solutions. All phosphorus-rich products show very good stability in strongly acidic media. The catalytic activity for hydrogen evolution ordered by higher current at a fixed electrode geometric area and low onset potential is CoP3 > NiP2 (cubic and monoclinic) > FeP2 >> CuP2. At high applied potentials, CuP2 undergoes surface reactions and roughening that improve its electrocatalytic activity. Correlations of the observed electrocatalytic activity with electrochemically active surface area, particle size, metallic versus semiconducting properties, and local metal coordination environment are noted for these phosphorus-rich 3d metal phosphides.