The persistent photoconductivity (PPC) in ZnO has been a critical problem in opto-electrical devices employing ZnO such as ultraviolet sensors and thin film transistors for the transparent display. While the metastable state of oxygen vacancy (V-O) is widely accepted as the microscopic origin of PPC, recent experiments on the influence of temperature and oxygen environments are at variance with the V-O model. In this study, using the density-functional theory calculations, we propose a novel mechanism of PPC that involves the hydrogen-zinc vacancy defect complex (2H-V-Zn). We show that a substantial amount of 2H-V-Zn can exist during the growth process due to its low formation energy. The light absorption of 2H-V-Zn leads to the metastable state that is characterized by the formation of O-2(2-) (peroxide) around the defect, leaving the free carriers in the conduction band. Furthermore, we estimate the lifetime of photo-electrons to be similar to 20 secs, which is similar to the experimental observation. Our model also explains the experimental results showing that PPC is enhanced (suppressed) in oxygen-rich (low-temperature) conditions. By revealing a convincing origin of PPC in ZnO, we expect that the present work will pave the way for optimizing optoelectronic properties of ZnO.