Galvanic replacement (GR) reactions involving active-metal nanoparticles (NPs) as seeds have a number of distinctive features and can produce various noble-metal nanoparticles. The oxide layer on the surfaces of such active-metal seeds may make a remarkable impact on the final products. Taking the Zn/Cu(2+) system as a model, we show that the GR reaction of pure Zn seeds with Cu(2+) ions leads to Cu nanodendrites, while oxide-covered Zn seeds result in ultrafine Cu NPs. We demonstrate here that the oxide layer does not block the GR reaction but slows down its rate. We also show that the growing Cu NPs can eventually detach from their ZnO substrate because of poor adhesion and disperse in the reaction liquid very well. Our studies provide detailed information on mechanisms of the GR reaction involving active-metal seeds, and therefore may be useful for further control of the morphology and properties of products prepared via this approach.