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Four samples of nominally pure KCl crystals and doped with Zn 2+ impurities are grown by the Czochralski method and characterized by X-ray diffraction and Proton Induced X-ray Emission techniques. Positron Annihilation Lifetime Spectroscopy (PALS) is performed to obtain information on the cation vacancy type defects and their evolution under doping. The results of the PALS experiment indicate that doping KCl by Zn 2+ ions, at first increases the concentration of mono vacancies and in the second stage leads the creation of divacancy sites. Coincidence Doppler Broadening Spectroscopy (CDBS) is carried out to obtain the chemical environment of positron annihilation sites. The results of CDBS show that cation vacancies have a significant role in the annihilation process. An interesting observation is the participation of Zn 2+ cations in the positron annihilation process which confirms that positrons are not completely localized on the anion sites. The internal consistency between the results of PALS and CDBS experiments is also clarified., (Copyright © 2020 Elsevier Ltd. All rights reserved.)