The electrodeposition of copper on the atomically smooth nitrogen-incorporated tetrahedral amorphous carbon (taC:N) electrode has been studied in basic ambient temperature AlCl3/1-ethyl-3-methylimidazolium chloroaluminate melts. A high overpotential for nucleation of copper on taC:N and no underpotential deposition features are observed, comparable to the behavior of boron-doped diamond electrodes. Electrochemical deposition and stripping of copper on taC:N show that most of the deposit is anodically dissolved only when the potential reaches that of Cu(I) oxidation in a system in which Cu(I) and Cu(II) are both stable. The low density of intrinsic active sites for nucleation and its early saturation with increasing overpotential are responsible for the slight deviation from a model of the ideal progressive type of nucleation at high overpotentials. (C) 2001 The Electrochemical Society. All rights reserved.