We report the discovery of a post-cotunnite phase of TiO2 by both density-functional ab initio calculations and high-pressure experiments. A pressure-induced phase transition to a hexagonal Fe2P-type structure (space group P6̄2m) was predicted to occur at 161 GPa and 0 K and successfully observed by in situ synchrotron x-ray diffraction measurements at 210 GPa and 4000 K with a significant increase in opacity. This change in opacity is attributed to a reduction of band gap from 3.0 to 1.9 eV across the phase change. The Fe2P-type structure is proved to be the densest phase in major metal dioxides. © 2011 American Physical Society.