A model is developed for estimating effects due to electron scattering from grain boundaries, occurring simultaneously with background scattering. Since grain‐boundary effects are negligible in bulk materials, the model is particularly relevant to polycrystalline metal films in which a very fine‐grained structure is often found. It is shown by solution of the appropriate Boltzmann equation, that the total resistivity can be strongly dominated by grain‐boundary scattering. If grain size increases with film thickness, a marked dependence of resistivity on thickness exists, even when scattering from external surfaces is negligible or is completely specular.