Epitaxial growth of single‐crystal Si films has been realized on the (100), (110), and (111) crystallographic planes of yttria‐stabilized, cubic zirconia single crystals. The Si films were grown by chemical vapor deposition, using the pyrolysis of at temperatures in the range 950°–1075°C and at deposition rates of 0.08–1.2 μm/min. A predeposition annealing procedure has been developed, resulting in a quasi‐stable, oxygen‐deficient zirconia surface. A model is presented to explain the dependence of oxygen kinetics in cubic zirconia on temperature and yttria content. The heteroepitaxial Si films have been characterized by optical and scanning electron microscopies, reflection electron diffraction, x‐ray diffraction, Rutherford backscattering and channeling, and surface electrical conductivity and Hall effect measurements. Several 0.4–0.5 μm thick (100)‐ and (110)‐oriented Si films on cubic zirconia were found to be of higher crystal quality than commercial (100) Si on sapphire films of similar thickness.