10.48788/DVUA/EHLZIT Tkach, Vira0000-0002-2403-8607(Frantsevich Institute for Problems of Materials Science of NAS of Ukraine)O.Y. Khyzhun0000-0001-6727-643X(Frantsevich Institute for Problems of Materials Science of NAS of Ukraine)N.M. Denysіuk0000-0002-0492-1945(Frantsevich Institute for Problems of Materials Science of NAS of Ukraine)Luzhnyi Ivan Vasyliovych0000-0003-3809-7517(Frantsevich Institute for Problems of Materials Science of NAS of Ukraine)Kopylova Kateryna Ihorivna0000-0001-6796-390X(Frantsevich Institute for Problems of Materials Science of NAS of Ukraine) DataverseUA 2026 This dataset contains survey, high-resolution core-level, and valence-band X-ray photoelectron spectroscopy (XPS) data obtained from the pristine surface of a TlPb2Br5 single crystal grown by the Bridgman–Stockbarger technique. The deposited files cover the Tl-4f, Pb-4f, and Br-3d core levels together with the valence-band region and include both numerical spectral data and corresponding graphical representations. The data can be used to examine the elemental composition, core-level electronic states, and valence electronic structure of the untreated TlPb2Br5 single-crystal surface. All deposited spectra correspond to the pristine surface. Tkach, Vira(Frantsevich Institute for Problems of Materials Science of NAS of Ukraine)Frantsevych Institute for Problems of Materials Science of NAS of Ukraine(N.A.S. of Ukraine)