We demonstrate the synthesis of Ag–NiO core–shell nanoflower arrays via a one-step solution-immersion process and subsequent RF-sputtering method. The aligned Ag nanoflower arrays on copper substrate are prepared by a facile displacement reaction in absence of any surfactant at a mild temperature. When used as anode materials for lithium-ion batteries, the Ag–NiO core–shell nanoflower arrays show better cycling performance and higher capacity than the planar NiO electrodes. The improved performance should be attributed to the core–shell structures that can enhance the conductivity and accommodate the volume change during the charge–discharge process.