In this work, N2H4 was used as surfacecapping agent for the first time to synthesize octahedral anatase TiO2 single crystals with dominant {101} facets from H0.68Ti1.83O 4 solid precursor. The resultant particle size of {101} facet enriched TiO2 was around 100 nm. The function of N2H 4 in the hydrothermal process is not only to provide a mild basic environment, but also to promote the growth of {101} surface because of its strong reducibility. The amount of N2H4 and precursor added in the solution is also investigated, and the result reveals that nearly 100 % {101} facet can be obtained only if N2H4 were added to a certain amount, while the concentration of precursor has no influence on the final result which means that this reaction can be largely scaled up. In oxygen evolution from photocatalytic water splitting, the {101} facets exhibited different performance using AgNO3 or (NH4) 2Ce(NO3)6 as sacrificial agent.