YBa2Cu3Ox (YBCO) films have been epitaxially grown on single-crystal YBCO (001) substrates by metalorganic chemical vapor deposition The YBCO substrates have a flat surface on an atomic scale. The compositional and structural changes of the YBCO substrate surface have been examined at various temperatures and oxygen pressures using Rutherford backscattering in channeling mode. The surface of YBCO substrate deteriorates above 400 C in oxygen pressures below 5 x 10^(-5) Torr. At high temperatures, like a deposition temperature, the surfaces are stable in limited oxygen pressures between 10^(-3) and one Torr. The YBCO substrates enhance the rate of step advance on a surface when the c-axis oriented YBCO film is deposited, resulting a step-like structure with a terrace width of 500 nm and unit-cell step height. The 2% Zn-doped YBCO is available as an N layer in an S/N/S junction, forming a YBCO (60 nm) / YBCO : Zn (12 nm) / YBCO (substrate) structure with a sharp Zn distribution.