An explicit model of contact‐charge exchange in polymers is proposed in which the steady‐state exchanged charge resides in intrinsic molecular‐ion states. The eigenvalue spectra of these states are inferred from metal/polymer contact‐charge measurements using a theoretical formalism constructed for this purpose. This model of metal/polymer contact‐charge exchange is extended to encompass the description of polymer/polymer contact‐charge exchange as well. Utilizing the metal/polymer contact‐charge‐exchange spectra as input data, the model predicts correctly both the sign and order of magnitude of measured contact‐charge exchange between polystyrene and copolymers of styrene and methyl methacrylate.