The effect of substrate temperatureTsduring evaporation on the microstructure of Pd2Si thin films on (111) Si formed by evaporation followed by subsequent higher‐temperature anneal has been investigated by transmission electron microscopy. ForTsof 20 and 100 °C, the Pd2Si grows epitaxially on the substrate. For aTsof 200 °C the Pd2Si is polycrystalline and grains are uniaxially textured about the [001] axis and there are pinholes in the film. For aTsof 300 °C, the microstructure of Pd2Si is spongy and grains are much less oriented.