A detailed light scattering investigation is presented on dilute solutions of long chain sodium polyacrylate in the presence of Cu2+ ions under conditions which are close to the precipitation threshold of the respective Cu2+-PA chains. The results are compared with literature data (Eur. Phys. J E 2001, 5, 117-126) from the corresponding system in the presence of Ca2+ ions. In all cases the solvent is a 0.1 M NaCl solution in water. The PA coils shrink considerably with increasing Cu2+ concentration as the conditions approach the precipitation threshold. Yet, the extent of shrinking can not be driven as far as for the respective Ca2+-PA system, where fully collapsed sphere-like polymers had been observed at the threshold. Analysis of the aggregation process with tune-resolved static light scattering reveals loose coil-like aggregate structures for Ca2+-PA aggregates and compact sphere-like aggregates for Ca2+-PA in accordance with the limiting shape of the respective shrunken single chains. The onset of Ca2+ or Ca2+ induced aggregation of PA chains at the precipitation threshold borders an intramolecular coil shrinking process. The transition of shrinking into aggregation occurs more readily with Ca2+-PA as it does with Ca2+-PA.