Nitrogen-doped graphene with metal-organic frameworks (N-G/MOFs) composites represent a new generation of hybrid materials that integrate the high conductivity and defect tunability of N doped graphene with the structural versatility, porosity, and catalytic potential of MOFs. This chapter presents a comprehensive overview of the physical and chemical structures of N-G/MOF composites, emphasizing how the combination of these two material systems results in enhanced electrochemical and physicochemical functionalities. It first discusses the intrinsic structural features of MOFs, including their crystallographic framework, porosity, thermal and mechanical stability, and tunable chemical composition, highlighting how these attributes influence their behaviour as precursors for hybrid formation. The discussion then shifts to the structural evolution of N-G/MOFs composites, which exhibit diverse morphologies such as MOF like, sandwich like, core shell, and complex architectures. The chapter explores how these morphologies, formed through various synthesis processes including high temperature carbonization or wet mechanochemical routes, determine the composites’ surface area, defect density, and electron transport characteristics. Furthermore, the chemical composition and functional groups within N-G/MOFs are examined, focusing on the roles of nitrogen functionalities, metal centres, metal oxides, oxygenated and sulfur species, phosphorus groups, and carbon moieties in defining catalytic and electrochemical activities. The synergistic interactions among these constituents are shown to enhance redox activity, conductivity, and stability, thereby improving overall performance in applications such as energy storage, catalysis, and environmental systems. By correlating structural attributes with electrochemical behaviour, this chapter provides a holistic understanding of how the architecture and chemical constitution of N-G/MOFs materials can be optimized for next generation energy technologies.