Directed transfer of carriers, akin to excited charges in photosynthesis, in semiconductors by structural design is challenging. Here, TiO2 nanosheets with interlayered sp2 carbon and titanium vacancies are obtained by low-temperature controlled oxidation calcination. The directed transfer of carriers from the excited position to Ti-vacancies to interlayered carbon is investigated and proven to greatly increase the charge transport efficiency. The TiO2/C obtained demonstrates excellent photocatalytic and photoelectrochemical activity and significant lithium/sodium ion storage performance. Further theoretical calculations reveal that the directional excited position/Ti-vacancies/interlayered carbon facilitate the spatial inside-out cascade electron transfer, resulting in high charge transfer kinetics. © 2022 The Royal Society of Chemistry.