The effect of intrinsic defect types and concentrations on the behaviors of exciton transitions and carrier transports in ZnO was investigated. The intrinsic acceptor-rich ZnO (A-ZnO) microtubes were grown by the developed optical vapor supersaturation precipitation. The oxygen growth carries gas (O₂) was used to realize the regulation of donor acceptor pair and neutral acceptor bound exciton A⁰X concentrations. The negative thermal quenching phenomenon was attributed to the middle energy state dominated by the defect concentrations. The abundant shallow acceptor concentrations and the middle energy state shifting up result in the electrical resistivity reduction by 7 times and the response time decreasing by 51% compared with the A-ZnO microtubes grown in air, leading to the high-efficient ultraviolet detector with high electrical resistivity. The present work provides a novel platform to optimize ZnO-micro/nanostructures-based optoelectronic devices.