Precursive iron films with different grain sizes were prepared by magnetron sputtering on substrates heated at different temperatures. The iron films were sulfurized at 673 K for 20 h to form pyrite films. The structural and electrical characters were determined. High substrate temperatures produce large crystallites in the precursive iron films. The pyrite films are composed of a surface layer with coarse columnar grains and a bottom layer with fine equiaxed grains. With the increase of iron grain scale, the carrier concentration decreases and the carrier mobility increases. The electrical resistivity of the pyrite films increases to a maximum in the precursive iron films with increasing the grain size to about 39 nm. Sufficient formation and growth of iron grains result in improved crystallinity and high continuity of the pyrite films. The crystal defect density, transformation stress level and atom diffusion behavior are responsible for the characteristics of the electrical properties dependent on the crystallinity and continuity of the pyrite films or the crystallizing status of the precursive iron films.