Co and Si have been codeposited on Si (111) substrates near room temperature in a stoichiometric 1:2 ratio in a molecular beam epitaxy system. Annealing of these deposits yields high‐quality single‐crystal CoSi2 layers. Transmission electron microscopy has been used to examine as‐deposited layers and layers annealed at 300, 500, and 600 °C. Single‐crystal epitaxial grains of CoSi2 embedded in a matrix of amorphous Co/Si are observed in as‐deposited samples, while the layer is predominantly single‐crystal, inhomogeneously strained CoSi2 at 300 °C. At 600 °C, a homogeneously strained single‐crystal layer with a high density of pinholes is observed. In contrast to other solid phase epitaxy techniques used to grow CoSi2 on Si (111), no intermediate silicide phases are observed prior to the formation of CoSi2.