Heteroepitaxial Si/CoSi2/Si structures have been synthesized by high‐dose implantation of Co into (100) and (111) Si at an energy of 170 keV and subsequent annealing. In the as‐implanted state the implanted Co is found to be present as CoSi2. For a dose of 2×1017Co/cm2, the Co is present in the form of epitaxial precipitates, which exhibit both the aligned (A‐type) CoSi2and twinned (B‐type) orientation. For a higher dose of 3×1017Co/cm2, a monocrystalline epitaxial CoSi2layer near the top of the implanted Co distribution is formed during the implantation. The heteroepitaxial structures that are formed in this way are fully aligned. In contrast, when these structures are formed by sequential surface deposition techniques, twinning occurs at every Si/CoSi2interface. The formation of the aligned orientation of the buried CoSi2layer can be attributed to the larger stability of aligned precipitates as compared to twin‐oriented precipitates.