The phase relation of the CuInSe2-CuSe pseudobinary system has been investigated. The solids in equilibrium with the liquids at temperatures above 630 degrees C are single-phase CuInSe2 with chalcopyrite structure, but those at temperatures below 630 degrees C are composed of two phases of CuInSe2 and Cu2-xSe. On the basis of the results, solution growth of CuInSe2 crystals is performed at similar to 780 degrees C using the Bridgman technique. The obtained crystals are of p-type conductivity, and the photoluminescence spectra exhibit a band-edge emission peaking at 1.04 eV.