Al/p‐CuInSe2Schottky contacts have been fabricated by vacuum‐depositing Al onto Bridgman‐grownp‐CuInSe2single crystals. The barrier heights from the temperature‐dependent forwardI‐Vcharacteristics are significantly less than theC−2‐Vintercepts. This is evidence of the presence of an interfacial layer and surface states in equilibrium withp‐CuInSe2. The barrier height, electron affinity, effective acceptor density, and relative Fermi potential as well as diffusion potential were estimated. The surface‐state density of the minimum order of 1012cm−2 eV−1was obtained for the etched CuInSe2surface. The transverse doping profile was qualitatively determined.