The room temperature positron annihilation lifetime for single crystalline ZnO has been measured as 164 ± 1 ps. The single component lifetime value is very close to but higher than the theoretically predicted value of ∼154 ps. Photoluminescence study (at 10 K) indicates the presence of hydrogen and other defects, mainly acceptor related, in the crystal. Defects related to a lower open volume than zinc vacancies, presumably a complex with two hydrogen atoms, are the major trapping sites in the sample. The bulk positron lifetime in ZnO is expected to be a little less than 164 ps.