Mg2Si/Si nanocomposites, consisting of Si nanosheet bundles and Mg2Si deposits formed on the Si nanosheet bundles, were formed by the thermal annealing of CaSi2 powders in MgCl2 vapor. Mg atoms are deposited on the Si nanosheet bundles, and the surface of the nanosheets were partially transformed into the Mg2Si phase during the thermal treatment. The Mg2Si/Si composites were also synthesized on Si(111) substrates. The structural and photoluminescence (PL) properties of the composites were characterized. The Mg2Si deposits were inhomogeneously distributed on the Si nanosheets. Furthermore, the Si-based nanosheets consisted of disordered thinner Si layers, and a disordered superlattice-like layered structural model is shown. The PL emissions in the visible region were clearly observed, and the temperature and the excitation intensity dependences of the emissions were characterized. It was found that the structural modification of the Si nanosheet bundles to form the composites with Mg2Si deposits affected the emission property of the Si nanosheets. The luminescence mechanism of the composite was discussed.