Superconducting YBaCuO thin films have been fabricated on single-crystal MgO by the spray-pyrolysis of nitrate precursors. The effects on the superconductive behavior of processing parameters such as time and temperature of heat treatment and film thickness were investigated. The superconductive behavior was found to be strongly dependent on film thickness. Films of thickness 1 μm were found to have a Tc of 67 K while thinner films showed appreciably degraded properties. Transmission electron microscopy studies have shown that the heat treatments necessary for the formation of the superconductive phase (for example, 950 °C for 30 min) also cause a substantial degree of film-substrate interdiffusion. Diffusion distances for Cu in the MgO substrate and Mg in the film were found to be sufficient to explain the degradation of the superconductive behavior in films of thickness 0.5 μm and 0.2 μm. From the concentration profiles obtained by EDS analysis diffusion coefficients at 950 °C for Mg into the YBaCuO thin film and for Cu into the MgO substrate were evaluated as 3 × 10−19 m2/s and 1 × 10−17 m2/s, respectively.