High temperature electrical conductivity (HTEC) as a function of temperature and component vapour pressure has been investigated in ZnS:Al and in CdSe:Al single crystals using a two zone resistance furnace and a vacuum sealed quartz ampoule with four tungsten or graphite electrodes. The activation energies of HTEC isobars and the slope values of HTEC isotherms in the large temperature region (500-1200 degreesC) and in a large component vapour pressure range were determined. The region of compensation of electrons with onefold ionized substitutional Al exists up to change with the region of self-compensation of native defects at high Cd vapour pressures in HTEC isotherms of CdSe:Al. These two electroneutrality conditions were never achieved in ZnS:Al crystals under investigation. The common feature for ZnS:Al isotherms at zinc vapour pressure and for CdSe:Al isotherms at selenium vapour pressure is the existence of self-compensation of Al defects. The equilibrium constant of the association of aluminium with cadmium vacancies in CdSe:Al was determined. The increasing role of holes appears similarly at low Zn vapour pressure values in ZnS:Al and at high selenium vapour pressure values in CdSe:Al. (C) 2004 Elsevier B.V. All rights reserved.