The photoexcited carrier lifetime in semiconductors plays a crucial role in solar energy conversion processes. The defects or impurities in semiconductors are usually proposed to introduce electron–hole (e–h) recombination centers and consequently reduce the photoexcited carrier lifetime. In this report, we investigate the effects of oxygen vacancies (OV) on the carrier lifetime in rutile TiO2, which has important applications in photocatalysis and photovoltaics. It is found that an OV introduces two excess electrons which form two defect states in the band gap. The lower state is localized on one Ti atom and behaves as a small polaron, and the higher one is a hybrid state contributed by three Ti atoms around the OV. Both the polaron and hybrid states exhibit strong electron–phonon (e–ph) coupling and their charge distributions become more and more delocalized when the temperature increases from 100 to 700 K. Such strong e–ph coupling and charge delocalization enhance the nonadibatic coupling between the electronic states along the hole relaxation path, where the defect states behave as intermediate states, leading to a distinct acceleration of e–h recombination. Our study provides valuable insights to understand the role of defects on photoexcited carrier lifetime in semiconductors.