Processes occurring on the plasma-facing walls in the Large Helical Device (LHD) and in-vessel material migration were investigated using a technique of material deposition probes. Ten Si plates were located on the outer side of the first-wall surface in each 36° toroidal section (Nos. 1–10). Mixed-material layers deposited on the probes during the fiscal year 2012 plasma campaign contained carbon, boron, hydrogen, and metals from which the plasma-facing elements were made. Metallic impurities and hydrogen content in deposited layers were examined by Rutherford backscattering spectrometry (RBS) and elastic recoil detection analysis (ERDA), respectively. The cross-sectional observations of the deposited mixed-material layers were performed with the help of a scanning electron microscope equipped with an energy dispersive X-ray (EDX) spectrometer. The results of the combined RBS/ERDA analysis and TEM-EDX examination allow tracing the processes occurring on plasma-facing components during the plasma campaign.