The composition, morphology and structure of the mixed layers deposited onto the surface (deposits) after a preliminary carboboronization procedure (B/C : H layers deposition) and subsequent plasma–wall interaction in the different areas of the Globus-M spherical tokamak have been analysed. Globus-M is almost completely covered by recrystallized graphite protection tiles (currently about 90% of its inner vessel area facing to plasma). The deposit properties were examined by different diagnostic techniques (electron probe microanalysis, scanning electron microscope, x-ray diffraction, nuclear resonance reactions, thermal desorption spectroscopy, infrared Raman scattering and secondary ion mass spectroscopy) after sample exposure to plasma during 3000–10000 tokamak pulses. It was found that deposits existed even in high flux regions (separatrix strike points). The initial composition of the protective layers formed during boronization is dramatically modified during long-term plasma–wall interaction and resulted in significant intermixing of its components with materials of the vessel interior. The properties of the layers deposited onto the surfaces intensively interacting with plasma, as well as the composition of the layers deposited in the 'shadowed' zones are discussed. Deuterium retention in Globus-M was estimated relying upon the data on deuterium concentrations in the deposits that were measured by different methods. It is revealed that deuterium was absorbed only in the deposits and its concentration vanished in the bulk of the tiles. Conditions of deuterium desorption are analysed and the merits of recrystallized graphite are discussed.