We have grown nickel heteroepitaxially on muscovite and synthetic mica in vacuo for use as substrates for scanning probe microscopy (SPM) and graphene formation. We have determined annealing conditions that could generate atomically flat surfaces (with rms surface roughness of less than 1 nm). Owing to accelerated degradation at temperatures above 600 °C, muscovite mica was unsuitable as a substrate at high growth temperatures. Thermally stable synthetic fluorophlogopite mica [KMg3(AlSi3O10)F2], on the other hand, was found to be stable at 800 °C and successfully employed for the formation of atomically flat films.