Layered TiO2 sheets with high Cr(VI) photoreduction ability were prepared by template free solvothermal method using ethylene glycol (EG) as structure directing agent. EG linking function in the layered TiO2 structure were confirmed by SEM, TEM, FTIR, XPS and so on. Moreover, the obtained large sized TiO2 (20~50 μm in length, about 5~10μm in width) were assembled by N‐doped TiO2 thin sheets with about 1.2nm gap in between, resulting in very high surface area (327.5 m2/g) and abundant Ti3+ sites for Cr(VI) adsorption and reduction. This structure can not only have good performance during Cr(VI) photocatalysis reduction application (Cr(VI) removal rate: 0.84 mg*g‐1*min‐1), but also endow the material with good cycle ability.