Hematite is a semiconducting mineral with a role in natural photoelectrochemical processes, and has been studied from the viewpoint of solar energy utilization. Hematite is an anisotropic conductor, with faster conduction parallel to (001) planes. Flatband potentials and photocurrent onset potentials for natural hematite single crystals and synthetic nanocrystalline hematite films are similar, and show Nernstian behavior within error. At pH 7, the flatband potential of single crystals is -0.25AE0.1 V vs. Ag/AgCl. Photocurrent onset potential is 0.02 to 0.03 V more negative for crystal faces than for crystal edges. Photocurrent density is a factor of 5 to 10 higher for crystal edges than for crystal (001) faces, presumably because of more rapid charge separation for the edges. Falling photocurrent transients decay more slowly for edges than for faces, consistent with more rapid removal of conduction band electrons into the bulk and therefore reduced availability of such electrons for back reaction. Rising photocurrent transients occur at higher potential, and have the same rise time for both faces and edges. This suggests that the rising transients are due to slow conduction through bulk hematite. The transition from falling to rising transients occurs at a more positive potential for edges than for faces, which is also consistent with more rapid charge transport away from edge surfaces and with Fermi level pinning at edges.