Thin films of the Tl‐based superconductors often have relatively poor properties because of film/substrate interdiffusion which occurs during the anneal. We have therefore investigated the use of BaF2 as a diffusion barrier. TICaBaCuO thin films were deposited by dc magnetron sputtering onto MgO <100> substrates, both with and without an evaporation‐deposited BaF2 buffer layer, and post‐annealed in a Tl over‐pressure. Electrical properties of the films were determined by four‐point probe analysis, and compositions were measured by ion‐backscattering spectroscopy. Structural analysis was performed by X‐ray diffraction and scanning electron microscopy. The BaF2 buffer layers were found to significantly improve the properties of the TICaBaCuO thin films.