Three-dimensional superhydrophobic/superlipophilic porous materials have attracted widespread attention for use in the separation of oil/water mixtures. However, a simple strategy to prepare superhydrophobic porous materials capable of efficient and continuous separation of immiscible and emulsified oil/water mixtures has not yet been realized. Herein, a superhydrophobic graphene/polystyrene composite material with a micro-nanopore structure was prepared by a single-step reaction through high internal phase emulsion polymerization. Graphene was introduced into the polystyrene-based porous materials to not only enhance the flexibility of the matrix, but also increase the overall hydrophobicity of the composite materials. The resulting as-prepared monoliths had excellent mechanical properties, were superhydrophobic/superoleophilic (water/oil contact angles were 151° and 0°, respectively), and could be used to continuously separate immiscible oil/water mixtures with a separation efficiency that exceeded 99.6%. Due to the size-dependent filtration and the tortuous and lengthy micro-nano permeation paths, our foams were also able to separate surfactant-stabilized water-in-oil microemulsions. This work demonstrates a facile strategy for preparing superhydrophobic foams for the efficient and continuous separation of immiscible and emulsified oil/water mixtures, and the resulting materials have highly promising application potentials in large-scale oily wastewater treatment.