Some interesting results concerning the structure and photoelectrochemical properties of anodically prepared lead oxide films on Pb electrodes in hot alkaline solution are described. When a Pb electrode is anodically polarized in a 0.1M NaOH + 0.1M Na2SO4 solution at 80 degrees C at high overpotentials, the alpha-PbO phase exclusively forms with a highly preferred orientation along the 110 plane. A nearly 14 mu m thick film with a high 110 orientation is obtained at potentials between -0.5 and +0.3 V vs. SCE. Further, anodic films obtained at these potentials show typical n-type semiconductivity with donor concentrations on the order of 10(15) cm(-3). In particular, the anodic film prepared at +0.3 V vs. SCE shows a solar-to-electrical-energy conversion efficiency of 1.55% and a very high quantum yield of nearly 80% for anodic photocurrent generation to visible monochromatic irradiation in 0.1M Fe(CN)(6)(3-/4-) electrolyte which are the highest values reported so far for lead oxide-based cells. A correlation has been found between the structure of the anodic film and its photoactivity.