Uniform and monodispersed TiO2 nanocrystals-assembled leaves-like nanosheets (TLNs) have been synthesized via a novel and direct hydrothermal method, i.e. a controlled hydrolysis of tetrabutyltitanate (TBOT) in ethanol without adding any surfactant reagents. The physical and chemical properties of TLNs were studied by field emission scanning electron microscopy, X-ray diffraction, high-resolution transmission electron microscopy, UV-Vis diffuse reflectance spectra and BET surface area measurement. The photoelectrochemical performance of TLNs was characterized through photocurrent and electrochemical impedance spectroscopy measurement. The photocatalytic activity of the TLNs was evaluated by photocatalytic reduction of Cr(VI) aqueous solution under simulated solar irradiation. The experimental results showed that the TLNs exhibited a much better photocatalytic activity than that of pure TiO2 (PT) and commercial TiO2 (P25). [GRAPHICS]