The thickness of 2D BiOCl nanosheets along [001] direction control the internal electric fields intensity. In order to enhance the photocatalytic properties of BiOCl, decreasing the thickness is the best choice. In this paper, black ultrathin BiOCl nanosheet (BU-BiOCl) with expanded spacing of the (001) crystal plane and oxygen vacancy was synthesized in high viscosity and alcohol group concentration glycerol system. It was characterized by X-ray diffraction patterns (XRD), X-ray photoelectron spectroscopy (XPS), X-ray photoelectron scanning electron microscope (SEM), high-resolution transmission electron microscopy (HRTEM), electron spin resonance (ESR), UV vis diffuse reflectance spectra (DRS) and photo-luminescence (PL) spectra. The experimental characterization and theoretical calculation results also indicated that expanded facets spacing and oxygen vacancy of as-synthesized BU-BiOCl enhanced separation efficiency of photoinduced carriers and photon absorption efficiency. Therefore, BU-BiOCl showed higher activity than bulk BiOCl for H-2 production under visible light irradiation. (C) 2015 Elsevier B.V. All rights reserved.