Iron phosphides were prepared by an economically feasible spray pyrolysis method, in which nontoxic and inexpensive precursors are used in an aqueous solution. The addition of NaCl to the precursor solution promoted crystal growth at a low temperature and helped to avoid sintering during posttreatment. The key conclusion is that the stoichiometry, shape, and size of the particles are related to the NaCl/Fe molar ratio and the posttreatment temperature. Below the melting temperature of NaCl, the shape and stoichiometry of the particles depended on the NaCl/Fe molar ratio, while above the melting temperature, they were dominated by the posttreatment temperature. Wire-like particles were formed at a NaCl/Fe molar ratio over 15.