Abstract In this paper the characterization of a thin (tens of nanometers) boron layer on fine grain polycrystalline graphite substrate is presented. The boron film is used as conditioning technique for the full graphite wall of the Reversed Field eXperiment–modified (RFX-mod) experiment, a device for the magnetic confinement of plasmas of thermonuclear interest. Aim of the present analysis is to enlighten the chemical structure of the film, the trapping mechanism that makes it a getter for oxygen and hydrogen and the reason of its loss of effectiveness after exposure to about 100 s of hydrogen plasma. X-ray Photoelectron Spectroscopy (XPS), Secondary Ions Mass Spectrometry (SIMS) and Fourier Transform Infra Red spectroscopy in combination with the Attenuated Total Reflectance (FTIR-ATR) were used to obtain the structure and the chemical composition of graphitic samples as coated or coated and subsequently exposed to hydrogen plasma after boron deposition. The boron layers on the only coated samples were found to be amorphous hydrogenated boron carbide plus a variety of bonds like B-B, B-H, B-O, B-OH, C-C, C-H, C-O, C-OH. Both the thickness and the homogeneity of the layers were found to depend on the distance of the sample from the anode during the deposition. The samples contained oxygen along the layer thickness, at level of 5%, bound to boron. The gettering action of the boron is therefore already active during the deposition itself. The exposure to plasma caused erosion of the boron film and higher content of H and O bound to boron throughout the whole thickness. The interaction of the B layer with plasma is therefore a bulk phenomenon.