Information on the chemical compatibility between Li ceramic breeders and reactor structural materials is an important issue for fusion reactor technology. In this work, Eurofer samples were placed inside a Li ceramic pebble bed and kept at 600 °C under a reducing atmosphere obtained by the flow of a purging gas (He+0.1vol.%H2). Titanate and orthosilicate Li pebble beds were used in the experiments and exposure time ranged from 50 to 2000 h. Surface chemical reactions were investigated with nuclear microprobe techniques. The orthosilicate pebbles present chemical reactions even with the gas mixture, whereas for the samples in close contact with Eurofer there is evidence of Eurofer elemental diffusion into the pebbles and the formation of different types of compounds. Although the titanate pebbles used in the chemical compatibility experiments present surface alterations with increasing surface irregularities along the annealing time, there is no clear indication of Eurofer constituents diffusion.