In this paper, a novel NiFe-LDH@ZnO composite was prepared by using a facile two-step process upon nickel foam (NF) substrate. The morphologies and chemical compositions of the samples were characterized by SEM, EDS, XRD and XPS. Photocatalytic degradation of Rhodamine B dye was tested with the samples NiFe-LDH@ZnO@NF, ZnO@NF and NiFe-LDH under the same conditions. The experimental results revealed that the NiFe-LDH@ZnO@NF composite exhibited excellent photocatalytic performance, i.e., 1.4 and 2.5 times higher than that of pure ZnO and NiFe-LDH, respectively. The reason was that the NiFe-LDH@ZnO@NF composite provided a possibility to effectively inhibit the recombination of the photogenerated electron-hole pairs, and therefore enhanced the photocatalytic efficiency. This composite is expected to have potential applications in wastewater treatment field.