This paper presents new water-soluble bio-polyelectrolyte-based nanoparticles, formed from lanthanide-induced polysaccharide aggregates (LIPAs). These new nano-aggregates are formed by coordinating a photoluminescent lanthanide–ligand complex to a single polyelectrolyte [i.e. polyanionic hyaluronic acid (HA)] or to two oppositely charged polyelectrolytes [i.e. HA and polycationic chitosan (CHI)]. We demonstrate that photoluminescent Eu3+–ligand complexes, which are dispersed homogeneously in aqueous solution by the association with water-soluble HA. The polysaccharide supermolecular assembly can be tuned to obtain nanoparticles of different sizes and surface charges. The preparation of stable and water-soluble lanthanide complexes via Eu3+–LIPAs opens opportunities for use of luminescent lanthanides in aqueous environments, for biosensing and bioimaging applications.