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Micro-/nano-characterization of the surface structures on the divertor tiles used in the first campaign(2011–2012) of the JET tokamak with the ITER-like wall (JET ILW) were studied. The analyzed tiles werea single poloidal section of the tile numbers of 1, 3 and 4, i.e., upper, vertical and horizontal targets,respectively. A sample from the apron of Tile 1 was deposition-dominated. Stratified mixed-materiallayers composed of Be, W, Ni, O and C were deposited on the original W-coating. Their total thicknesswas ∼1.5 m. By means of transmission electron microscopy, nano-size bubble-like structures with asize of more than 100 nm were identified in that layer. They could be related to deuterium retention inthe layer dominated by Be. The surface microstructure of the sample from Tile 4 also showed deposition:a stratified mixed-material layer with the total thickness of 200–300 nm. The electron diffraction patternobtained with transmission electron microscope indicated Be was included in the layer. No bubble-likestructures have been identified. The surface of Tile 3, originally coated by Mo, was identified as the erosionzone. This is consistent with the fact that the strike point was often located on that tile during the plasmaoperation. The study revealed the micro- and nano-scale modification of the inner tile surface of the JETILW. In particular, a complex mixed-material deposition layer could affect hydrogen isotope retentionand dust formation.