Graphene (GN)-related nanomaterials such as graphene oxide, reduced graphene oxide, quantum dots, etc., and their composites have attracted significant interest owing to their efficient antimicrobial properties and thus newer GN-based composites are being readily developed, characterized, and explored for clinical applications by scientists worldwide. The GN offers excellent surface properties, i.e., a large surface area, pH sensitivity, and significant biocompatibility with the biological system. In recent years, GN has found applications in tissue engineering owing to its impressive stiffness, mechanical strength, electrical conductivity, and the ability to innovate in two-dimensional (2D) and three-dimensional (3D) design. It also offers a photothermic effect that potentiates the targeted killing of cells via physicochemical interactions. It is generally synthesized by physical and chemical methods and is characterized by modern and sophisticated analytical techniques such as NMR, Raman spectroscopy, electron microscopy, etc. A lot of reports show the successful conjugation of GN with existing repurposed drugs, which improves their therapeutic efficacy against many microbial infections and also its potential application in drug delivery. Thus, in this review, the antimicrobial potentialities of GN-based nanomaterials, their synthesis, and their toxicities in biological systems are discussed.