The photoresponse of natural mineral pyrite and galena electrodes has been studied in aqueous solutions on freshly fractured surfaces (some fractured in situ) using moderate overvoltages. When fractured in situ, the electrode potential of both minerals instantly drops several tenths of a volt. Pyrite exhibits a spontaneous anodic photocurrent at fracture, which indicates upward band bending (depletion layer) on the n-type electrodes. The negative surface charge responsible for the depletion layer is believed to arise from a surface state that is intrinsic to pyrite surfaces, possibly modified by hydroxide ion adsorption. The flat band potential, Vty, of pyrite is at approximately -1.0 V (SCE) at pH 9.2 but to reach V(b, pyrite has to be cathodically decomposed. In contrast, galena assumes the flat band potential at fracture. Subsequent polarisation of galena at potentials positive of Vth produces an anodic photocurrent (upward band bending) and polarisation negative of Vro a cathodic photocurrent. Most of the galena electrodes studied were degenerate n-type and at potentials negative of Vtb, no cathodic photocurrents are observed, indicating the bands cannot be bent downward, consistent with the Fermi level at the surface merging with the conduction band edge near Vn,. Several were close to intrinsic, with the photocurrent changing sign near Vn,.