The structure of composite oxide films on aluminum has been investigated by scanning electron microscopy (SEM) of fractured sections and by transmission electron microscopy (TEM) of ultramicrotomed sections. It was found that TEM of ultramicrotomed sections is an extremely powerful technique for structural examination of the composite oxide films at high resolution. Voids and cracks, which are responsible for an electrical instability so-called “relaxation”, could be observed clearly within the composite oxide films. Although, the voids and cracks could not be observed readily by SEM of fractured sections due to the limited resolution, SEM has an important advantage that it allows ready examination over wide areas of the specimen. Various types of defects, introduced during relaxation, could be observed readily by SEM. Thus, the combination of the both techniques allows a more complete picture to be obtained on the structure of the composite oxide films of practical importance for capacitor applications.