CuInSe2 crystals with a single phase of chalcopyrite structure and homogeneous compositions have been grown by synthesis solute diffusion method with controlling the growth rate. The Cu/In ratio seems to increase as the temperature of crystal growth increases and is close to unity as the temperature of Se source increases. The results of the temperature dependence of the Hall effect for n- and p-type crystals indicate that the accepters of about 40 and 80 meV are due to Cu in In-site and In-vacancies and the donor of 10-20 meV is due to Se-vacancies, as compared with the photoluminescence spectra and compositional variations.