Metal–organic framework (MOF) and graphene oxide (GO) composite materials (MOF/GO) have been regarded as promising for separation applications due to their synergistically enhanced adsorption properties. Molecular-level understandings of these materials, however, remain unknown to date. In this study, molecular simulations were used, for the first time, to model these composite materials. Specifically, the composite MOF-5/GO material was modeled as stacks of sandwich-like layers on top of one another, consistent with experimental observations inferred from XRD and the SEM images. Simulations indicate that CO₂ and CH₄ bind strongly in the MOF/GO interface region, resulting in synergistically enhanced adsorption properties. To exploit the interface region, we found that in simulating linear alkanes, larger guest molecules show substantially improved adsorption properties in composites compared to the parent MOF-5 structure, illustrating that the performance of adsorption in these molecules will benefit the most from the MOF/GO composites.