Cations interacting specifically with anionic polyacrylates (PA) typically cause precipitation thresholds at stoichiometric amounts of cations per anionic residue. Contrary to this, Ag+ cations generate a much more complex phase behavior, where a regime of aggregation sets in at extremely low Ag+ contents and where a re-entrant phase with stable Ag-PA entities, 25-50 nm in size, occurs at intermediate Ag+ contents in between the aggregation regime and the precipitation threshold. The present proposal focusses on the structural analysis of these small stable entities, which may play an important role if applied in assisted Ag-nanoparticle formation.