MgO films were epitaxially grown on single crystal MgO substrates by atmospheric-pressure chemical vapor deposition (CVD). Reciprocal lattice mappings and X-ray reflection pole figures were used to evaluate the crystal quality of the synthesized films and their epitaxial relation to their respective substrates. The X-ray diffraction profiles indicated that the substrates were oriented out-of-plane during MgO crystal growth. Subsequent pole figure measurements showed how all the MgO films retained the substrate in-plane orientations by expressing the same pole arrangements. The reciprocal lattice mappings indicated that the whisker film showed a relatively strong streak while the continuous film showed a weak one. Hence, highly crystalline epitaxial MgO thin films were synthesized on single crystal MgO substrates by atmospheric-pressure CVD.