We employed high‐energy ball‐milling technique to fabricate TiO/TiO2 heterogeneous nanostructures. XRD proved the existence of TiO/TiO2 heterogeneous structures. SEM and HRTEM investigation evidenced that the mean particle size and mean grain size of the as‐prepared samples are 23 nm and 13 nm, respectively. UV‐Vis spectra exhibited that TiO has enhanced the visible light absorption of TiO2 and has changed the Eg of TiO2. UPS examination indicated that the electron work function (EWF) of TiO is higher than that of TiO2. Photocatalytic degradation experiments revealed that an appropriate TiO content can enhance the photocatalytic activity of pure anatase TiO2. The best photocatalytic activity of TiO/TiO2 heterogeneous nanostructures is even better than that of Au‐deposited TiO2 by keeping high degradation efficiency of 93%. The internal electrical field producing in TiO/TiO2 heterogeneous nanostructures was considered to be dominantly responsible for the enhanced photocatalytic activity. Therefore, the substitution of TiO with noble metal in TiO2 will be widely used in the future due to its low cost. This study also provides a clear direction of enhancing photocatalytic activity of TiO2: incorporating a guest compound into TiO2 with an appropriate content if the compound has much higher electron work function than that of TiO2.