The paper reviews black chromium electrodeposited from a trivalent chromium bath containing ZnO as a second main component. The chemical compositions of the top layers of the black chromium coatings were studied by the X-ray photoelectron spectroscopy method. The surface of black chromium was found to be almost entirely covered with organic substances. To gain information on the state of each element in the deposit bulk, the layer-by-layer etching of the black chromium surface with argon gas was used. Analysis of XPS spectra has shown that the top layers of black chromium without zinc are composed of various Cr(III) components, organic substances and metallic Cr, whereas metallic Cr is almost absent in black chromium containing some amount of Zn(II) compounds. The ratios of metal/oxide phases were found to be 10/27 and 2/28 for black chromium without and with zinc, respectively. It has been determined that owing to the presence of ZnO in the Cr(III) bath, the percentage of metallic chromium is substantially reduced in black chromium which is quite important for good solar selective characteristics of the coating. The results confirm some of earlier observations and provide new information on the composition of the near-surface layers. (C) 2014 Elsevier B.V. All rights reserved.