Anisotropy microellipsometry (AME) and photoresist microelectrochemistry were applied simultaneously to study the anodic film formation on the optically anisotropic valve metals zirconium and titanium. All measurements were performed in situ (0.5 M H2SO4) on single-substrate grains of technically relevant polycrystalline material. In addition to standard parameters, such as the film thickness and the optical constants of substrate and layer, AME yields the angle phi between the optical axes of the samples and the surface normals. This allows a. quantitative correlation of the microelectrochemically measured film properties with the crystallographic orientation of substrate grains. It was found that the properties of both TiO2 and ZrO2 films vary with the grain orientation in a systematic manner. For Ti, a significant increase of the thickness along with a decrease of the defect state density of the 12-type semiconducting TiO2 films with increasing substrate angle phi was observed. The TiO2 films were amorphous on all grains. In contrast, the ZrO2 films were crystalline on all grain surfaces but the (0001) orientation which is the closest-packed one (phi = 0 degrees).