Ion partitioning behavior in electrolyte solutions plays an important role in drug delivery and therapeutics, protein folding, materials science, filtration, and energy applications such as supercapacitors. Here, we show that the segregation of ions in solutions also plays an important role in the exfoliation of natural flake graphite to pristine graphene. Polarizable anions such as iodide and acetate segregate to the interfacial region of the aqueous phase during solvent interfacial trapping exfoliation of graphene. Ordered water layers and accumulated charges near the graphene surface aid in separating graphene sheets from bulk graphite, and, more importantly, reduce the reversibility of the exfoliation event. The observed phenomenon results not only in the improved stability of graphene-stabilized emulsions but also in a low-cost and environmentally friendly way of enhancing the production of graphene.