The assembly of graphene derivatives and inorganic nanostructures opens up an exciting new field in the functionalization of nanomaterials. However, a better understanding of the interaction between graphene derivatives and inorganic precursors remains a challenge. This work provides an efficient strategy for exploring this interaction by first modifying graphene oxide with aniline, glycine, and glycyl glycine, respectively, and thus engineering the chemical microenvironments on graphene sheets for anchoring metal ions. After that, the affinities of graphene derivatives to various metal ions can be investigated with the help of a conventional electrochemical method. The method highlights the importance of graphene chemistry in hybrid preparation and provides design principles for chemical modifiers used in the construction of multifunctional carbon–inorganic nanostructures.