With the development and application of graphene oxides (GO), the potential toxicity and environmental behavior of GO has become one of the most forefront environmental problems. Herein, a novel nanoscale layered double hydroxides (glycerinum-modified nanocrystallined Mg/Al layered double hydroxides, LDH-Gl), layered double oxides (calcined LDH-Gl, LDO-Gl) and metallic oxide (TiO2) were synthesized and applied as superior coagulants for the efficient removal of GO from aqueous solutions. Coagulation of GO as a function of coagulant contents, pH, ionic strength, GO contents, temperature and co-existing ions were studied and compared, and the results showed that the maximum coagulation capacities of GO were LDO-Gl (448.3 mg g−1) > TiO2 (365.7 mg g−1) > LDH-Gl (339.1 mg g−1) at pH 5.5, which were significantly higher than those of bentonite, Al2O3, CaCl2 or other natural materials due to their stronger reaction active and interfacial effect. The presence of SO32− and HCO3− inhibited the coagulation of GO on LDH-Gl and LDO-Gl significantly, while other cations (K+, Mg2+, Ca2+, Ni2+, Al3+) or anion (Cl−) had slightly effect on GO coagulation. The interaction mechanism of GO coagulation on LDO-Gl and TiO2 might due to the electrostatic interactions and strong surface complexation, while the main driving force of GO coagulation on LDH-Gl might be attributed to electrostatic interaction and hydrogen bond, which were further evidenced by TEM, SEM, FT-IR and XRD analysis. The results of natural environmental simulation showed that LDO-Gl, TiO2 or other kinds of natural metallic oxides could be superior coagulants for the efficient elimination of GO or other toxic nanomaterials from aqueous solutions in real environmental pollution cleanup.