Carbothermal reduction of semiconducting TiO2 into highly conductive titanium oxycarbide (TiOxCy) was investigated. The thermally produced uniform carbon layer on TiO2 (Degussa P25) protects the TiO2 nanoparticles from sintering and, at the same time, supplies the carbon source for doping TiO2 with carbon. At low temperatures (e.g., 700 °C), carbon only substitutes part of the oxide and distorts the TiO2 lattice to form TiO2−xCx with only substitutional carbon. When the carbon-doped TiO2 is annealed at a higher temperature (1100 °C), x-ray diffraction and x-ray photoelectron spectroscopy results showed that TiOxCy, a solid solution of TiO and TiC, was formed, which displays different diffraction peaks and binding energies. It was shown that TiOxCy has much better oxygen revolution reaction activity than TiO2 or TiO2−xCx. Further studies showed that the TiOxCyobtained can be used as a support for metal electrocatalyst, leading to a bifunctional catalyst effective for both oxygen reduction and evolution reactions.