[en] Understanding the interaction between graphene and its supporting substrate is of paramount importance for the development of graphene based applications. In this work the interplay of the technologically relevant graphene–Cu system is investigated in detail as a function of substrate grain orientation in Cu polycrystalline foils. While (1 0 0) and (1 1 1) Cu grains show the well-known graphene-enhanced oxidation, (1 1 0) grains present a superior oxidation resistance compared to uncovered Cu and an anomalous shift of its graphene 2D Raman band which cannot be explained by the known effects of strain and doping. These results are interpreted in terms of a weak graphene–Cu coupling at the (1 1 0) grains, and show that graphene can actually be used as anticorrosion coating, contrary to previously reported. The anomalous shift is suggested to be the result of an enhanced outer Raman scattering process which surpasses the usually dominant inner process. Since Raman spectroscopy is widely used as first and main characterization tool of graphene, the existence of an anomalous shift on its 2D band not only challenges the current theory of Raman scattering in graphene, but also has profound implications from an experimental point of view. (paper)