The formation of good quality epitaxialc‐axis‐perpendicular YBa2Cu3O7superconducting thin films on (100) yttria‐stabilized‐zirconia (YSZ) substrates in the temperature range of 550–650 °C by a biased laser deposition method is reported. However, below 550 °C, the epitaxial quality of the films decreased appreciably with corresponding changes in the superconducting properties. For temperatures much below the critical temperature, the critical current density showed a linear variation with temperature, with a value of 1.0×106A/cm2at 77 K and zero magnetic field. Because of the lattice mismatch between the substrate and the film, the interface was found to be highly strained in the presence of a large number of defects. The epitaxial nature and the crystalline quality of the films were determined by a number of techniques including Rutherford backscattering/channeling, electron channeling, cross‐section transmission electron microscopy (TEM), and x‐ray diffraction techniques. Rutherford backscattering channeling showed a minimum channeling yield of about 18%–25% for films deposited at and above 550 °C. Cross‐section TEM and x‐ray diffraction revealed the following thin film and substrate relationships: [001]film∥[001]YSZand [110]film∥[100]YSZ. The electron channeling pattern taken from a large area confirmed the epitaxial relationship. The lattice parameters mismatch in this orientation has been found to gives rise to stresses near the interface.