For the first time, silicate‐substituted hydroxyapatites have been prepared from mixtures containing different amounts of silicon (0.2–2 mol per mol of apatite unit cell) by dry mechanochemical synthesis at room temperature in a planetary ball mill. The XRD, FTIR, TEM, and NMR spectroscopic data show that the product of the mechanochemical synthesis is a single‐phase nanocrystalline apatite containing different amounts of carbonate and silicate ions and adsorbed water. In the annealed samples, three silicon concentration subranges can be distinguished, each of which is characterized by specific evolution of the lattice parameters. The formation mechanism of the silicate‐substituted hydroxyapatite obtainable by this method is discussed. The studies indicate that the silicon substitution limit in the silicate‐substituted lattice achievable by the dry mechanochemical synthesis followed by heat treatment is 1.2 mol per mol of apatite unit cell.