Development of applications for graphene are currently hampered by its poor dispersion in common, low boiling point solvents. Covalent functionalization is considered as one method for addressing this challenge. To date, approaches have tended to focus upon producing the graphene and functionalizing subsequently. Herein, we describe simultaneous electrochemical exfoliation and functionalization of graphite using diazonium salts at a single applied potential for the first time. Such an approach is advantageous, compared to postfunctionalization of premade graphene, as both functionalization and exfoliation occur at the same time, meaning that monolayer or few-layer graphene can be functionalized and stabilized in situ before they aggregate. Furthermore, the N2 generated during in situ diazonium reduction is found to aid the separation of functionalized graphene sheets. The degree of graphene functionalization was controlled by varying the concentration of the diazonium species in the exfoliation solution. The formation of functionalized graphene was confirmed using Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The functionalized graphene was soluble in aqueous systems, and its solubility was 2 orders of magnitude higher than the nonfunctionalized electrochemically exfoliated graphene sheets. Moreover, the functionalization enhanced the charge storage capacity when used as an electrode in supercapacitor devices with the specific capacitance being highly dependent on the degree of graphene functionalization. This simple method of in situ simultaneous exfoliation and functionaliztion may aid the processing of graphene for various applications.