In this paper, we have experimentally investigated the theoretical predictions of VO-Zni to be a native donor in ZnO. Intrinsically zinc-rich n-type ZnO thin films having ND ∼ 6.23 × 1018 cm-3 grown by molecular beam epitaxy on Si (0 0 1) substrate were annealed in oxygen environment at 500-800 °C, keeping a step of 100 °C for 1 h, each. Room temperature Hall measurements demonstrated that free donor (VO-Zni) concentration decreased exponentially and Arrhenius plot yielded activation energy to be 1.2 ± 0.01 eV. This value is in agreement with theoretically reported activation energy of VO-Zni donor complex in ZnO. We argue; this observation can be explained by two-step process: (i) incoming oxygen fills VO of VO-Zni complex leaving behind Zni; (ii) Zni releases its energy and moves to a lower energy state with respect to the conduction band minima and/or occupies an inactive location. Consequently, Zni-VO complex loses its donor role in the lattice. Our experimental data supported theoretical predictions of VO-Zni to be a native donor. Results from photoluminescence spectroscopy carried out on Zn-rich ZnO additionally justify the existence of VO-Zni complex. © 2013 IOP Publishing Ltd.