The bismuthates (for example, Ba1-xKxBiO3) represent a class of high transition temperature superconductors. The lack of anisotropy and the long coherence length of the bismuthates makes them technologically interesting for superconductor device applications. To obtain (100) oriented Ba1-xKxBiO3 films on (100) oriented MgO, a two-stage deposition process is utilized. In the first stage the films are nucleated at higher substrate temperatures, without the potassium. This process appears to facilitate the formation of the perovskite (100) orientation on (100) MgO. This nucleation layer is typically between 10 and 50 nm thick. In the second stage, the substrate temperature is reduced and the Ba1-xKxBiO3 is grown. Continued growth of (100) oriented material is possible at the lower substrate temperature.