In this paper, we propose a chemically grown titanium oxide (TiO₂) on Si to form a heterojunction for photovoltaic devices. The chemically grown TiO₂ does not block hole transport. Ultraviolet photoemission spectroscopy was used to study the band alignment. A substantial band offset at the TiO₂/Si interface was observed. X-ray photoemission spectroscopy (XPS) revealed that the chemically grown TiO₂ is oxygen-deficient and contains numerous gap states. A multiple-trap-assisted tunneling (TAT) model was used to explain the high hole injection rate. According to this model, the tunneling rate can be 10⁵ orders of magnitude higher for holes passing through TiO₂ than for flow through SiO₂. With 24-nm-thick TiO₂, a Si solar cell achieves a 33.2 mA/cm² photocurrent on a planar substrate, with a 9.4% power conversion efficiency. Plan-view scanning electron microscopy images indicate that a moth-eye-like structure formed during TiO₂ deposition. This structure enables light harvesting for a high photocurrent. The high photocurrent and ease of production of chemically grown TiO₂ imply that it is a suitable candidate for future low-cost, high-efficiency solar cell applications.