A novel composite composed of exfoliated graphene nanoplatelets (Ex-GNPs) incorporated in a MIL-100(Fe) framework has been synthesized using an in situ molecular-level interaction approach. The resulting Ex-GNP/MIL-100(Fe) composite, with varying Ex-GNP contents, has been characterized for microstructure, degree of crystallinity, thermal stability, water sorption behavior, and hydrothermal cyclic stability.