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Electrically insulating objects gain a net electrical charge when brought in and out of contact. This phenomenon—triboelectricity—involves the flow of charged species, but conclusively establishing their nature has proven extremely difficult. Here, we demonstrate an almost linear relationship between a plastic sample’s net negative charge and the amount of solution metal ions discharged to metallic particles with a coefficient of proportionality linked to its electron affinity (stability of anionic fragments). The maximum magnitude of reductive redox work is also material dependent: metallic particles grow to a larger extent over charged dielectrics that yield stable cationic fragments (smaller ionization energy). Importantly, the extent to which the sample can act as electron source greatly exceeds the net charging measured in a Faraday pail/electrometer set up, which brings direct evidence of triboeletricity being a mosaic …