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Phosphoric acid is an inorganic acid used for producing graphene sheets by delaminating graphite in (electro-)chemical baths. The observed phenomenology during the electrochemical treatment in phosphoric acid solution is partially different from other acidic solutions, such as sulfuric and perchloric acid solutions, where the graphite surface mainly forms blisters. In fact, the graphite surface is covered by a thin layer of modified (oxidized) material that can be observed when an electrochemical potential is swept in the anodic current regime. We characterize this particular surface evolution by means of a combined electrochemical, atomic force microscopy and Raman spectroscopy investigation.