Graphene oxide (GO) nanosheets have been experimentally proved to be a highly efficiency, rapid and universal demulsifier to break up the crude oil-in-water emulsion and/or the emulsified oily waste water in our previous study. To recycle the GO nanosheets and avoid the possible contamination of GO for crude oil, in this work, the magnetic graphene oxide (M-GO) was successfully synthesized and used for separating oil/water emulsions. Demulsification tests indicated that M-GO could separate the oil/water emulsions within a few minutes and recycle 6–7 times without losing its demulsification capability. The residual oil content in the separated water was as low as ∼10 mg/L, corresponding to a demulsification efficiency of 99.98% at an optimal dosage. Quantum chemical calculation results indicated that the π-π/σ-π interactions between GO materials and asphaltene molecules are the major driven forces for the high demulsification performance of M-GO nanosheets. This work not only provides a promising demulsifies to demulsify the crude oil-in-water emulsion or the oily wastewater but also give a deep understanding on the intrinsic interaction between demulsifiers and asphaltenes.