A new approach is presented, based on the unexpectedly versatile role of transition metal ions, to produce high‐quality graphene via an anodic electrochemical exfoliation route, and the capability of the resultant material in energy storage applications are illustrated. The method is based on graphene exfoliation in the presence of transition metals (Co2+ and Fe3+) which act as antioxidants, preventing surface oxidation of graphene, while other metals (Ru3+, Mn2+, Ir3+, and Sn4+) act as metal oxide decorators. The addition of Co2+ ions to the exfoliation solution produced few‐layer graphene that is two orders of magnitude more conducting and contains 80% less oxygen than the material obtained in the absence of cobalt ion. By contrast, the use of Mn2+ and Ru3+ in the electrolyte form an interconnected honeycomb lamellar structure of MnO2 and RuO2 nanoparticles, respectively. The combination of Mn2+ and Ru3+ create a uniformly grown Ru–Mn oxide hybrid structure on the graphene sheets in a single stage process, which is found to be an efficient electrode for supercapacitors (specific capacitance of 500 F g−1) and as a bifunctional water splitting electrocatalyst. The use of these inexpensive salts will aid the scalable production of high‐quality graphene and functionalized graphene for diverse applications.