Rare-earth ion-doped ZnO has been the focus of numerous investigations because of its unique optical properties and promising applications in optoelectronic devices. Here we presented a facile electrochemical deposition route for the controllable preparation of Eu3+/ZnO nanostructures on a large scale. The prepared Eu3+/ZnO deposits were characterized by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, selected area electron diffraction, and X-ray photoelectron spectroscopy. Herein, the growth mechanisms of Eu3+/ZnO nanosheets and nanorods were discussed. The formation process of Eu3+/ZnO foam-like nanostructures is illuminated in this paper. The room temperature photoluminescence properties of the Eu3+/ZnO foam-like nanostructures were investigated. The sharp 4f-4f transition emissions of Eu3+ can be directly observed at 593, 617, and 698 nm. An energy transfer between ZnO and Eu3+ is shown to occur under UV excitation.