Metal deposition and dissolution on diamond and diamond-like materials have different characteristics than on metallic electrodes and typical graphitic carbons. The behavior of copper on the recently developed tetrahedral amorphous carbon incorporating nitrogen (taC:N) film materials is addressed with quantitative speciation and voltammetry through rotating ring-disk electrode techniques. The nearly atomically smooth and widely stable taC:N film on polished Si wafers shows high nucleation overpotentials for copper deposition followed by anodic dissolution requiring participation of both the stable Cu(I) and Cu(II) states present in chloride media. The adhesion of copper films plated from conventional sulfate baths is strongly dependent on transport conditions. The anodic characteristics of the deposits reflect both the difficult nucleation process and the relative inertness of the taC:N interface. (C) 2001 The Electrochemical Society. All rights reserved.