A kinetic study of the electroless deposition of copper on gold, using dimethylamine borane (DMAB) as a reducing agent, has been carried out. The copper deposition rate in the electroless bath was determined to be 50 nm min-1, through electrochemical stripping of the copper deposits as well as from direct measurements of the film thickness using atomic force microscopy (AFM). Comparison with a galvanic cell setup, where the two half-reactions were physically separated, yielded a lower deposition rate of 30 nm min-1. An important kinetic effect of the surface on the oxidation of the reducing agent, and thus on the overall process, was therefore revealed. The efficiency of the process was measured over time, revealing the contribution of side reactions in the cathodic half-cell, particularly during the initial stages of the electroless process. © 2010 American Chemical Society.