The RbPb2Br5 crystal has been grown by Bridgman method. The electronic structure of RbPb2Br5 has been measured with XPS for a powder sample. High chemical stability of RbPb2Br5 surface is verified by weak intensity of O 1s core level recorded by XPS and structural RHEED measurements. Chemical bonding effects have been observed by the comparative analysis of element core levels and crystal structure of RbPb2Br5 and several rubidium- and lead-containing bromides using binding energy difference parameters Delta(Rb) = (BE Rb 3d - BE Br 3d) and d Delta(Pb) = (BE Pb 4f(7/2) - BE Br 3d). (C) 2011 Elsevier B.V. All rights reserved.