In this critical review, new nanomaterials based on graphene (GN) are described, especially those used for the assembly of miniaturized electrochemical transducers. In particular, the physicochemical properties and mechanical features of few layers of graphene (FLGs) are described, as is their use for assembly of chemically modified sensors, biosensors, and immunosensors. The FLGs described here were functionalized by chemical treatment in solution, resulting in oxidized and/or reduced surfaces, edges, and sides. The presence of oxygenated functionality strongly affects the electrocatalysis and the electron-transfer properties of several molecular targets, not only in the solid phase (e.g. in field-effect transistors, FETs) but also in liquid matrices (chemically modified electrodes and biosensors). In addition, "green chemistry" reagents, for example ionic liquids (ILs) can be used for exfoliation and intercalation of graphene planes, to obtain stable and homogeneous nanodispersions. The assembled sensors, biosensors, and immunosensors are extremely useful for electrochemical detection of several electro-active targets of importance in food analysis, environmental monitoring, and clinical diagnosis. A detailed description of each analytical application has been given in this critical review and brief remarks on the emerging disciplines of nanomedicine and nanofoods are also discussed.