Three-dimensional (3D) hierarchical graphene oxide-NiFe layered double hydroxide (GO-NiFe LDH) composite with sandwich-like structure is fabricated using a facile one-pot hydrothermal reaction. Electron microscopy images demonstrate that the GO-NiFe LDH composite possesses a highly porous and well-ordered structure. Both sides of the GO are fully covered by the LDH nanosheets, resulting in the sandwich-like architecture. The adsorption performance of the GO-NiFe LDH composite and pure NiFe LDH for three anionic pollutants, namely, Congo red (CR), methyl orange (MO) and hexavalent chromium ion [Cr(VI)] is systematically investigated. The presence of GO in the GONiFe LDH composite leads to the better adsorption capability and faster adsorption kinetics of this composite compared with the NiFe LDH microspheres. The pseudo-second-order kinetic model can well represent the adsorption kinetics, and the Langmuir isotherm model provides a better description for the adsorption isotherms. The GO-NiFe LDH composite demonstrates appreciable potential in alleviating anionic pollutants from the aquatic environment as shown by its excellent adsorption capability towards CR, MO and Cr(VI).