Single crystal of KPb2Br5 has been grown using the Bridgman technique. Initially the synthesis of stoichiometric KPb2Br5 compound was performed from high purity bromide salts. Electronic structure of KPb2Br5 has been determined with X-ray photoelectron spectroscopy for powdered sample fabricated by grinding in air. Drastic chemical interaction of KPb2Br5 with atmosphere has not been detected. Chemical bonding in potassium- and lead-containing bromides is considered using binding energy differences Delta(K)=(BE K 2p(3/2) - BE Br 3d) and Delta(pb)=(BE Pb 4f(7/2) - BE Br 3d), respectively, as representative parameters. (C) 2010 Elsevier B.V. All rights reserved.