We report on the gelation capability of polystyrene/poly(2-vinyl pyridine) amphiphilic heteroarm polyelectrolyte stars in acidic salt-free aqueous media. The star polymers associate through hydrophobic interactions, by retraction of the stretched arms under no interdigitation conditions, in the dilute regime forming colloidal soft nanoparticles comprising about 6 stars, At concentrations significantly higher than the hydrodynamic overlap concentration (c> 40c*), the crowding of the colloidal nanoparticles drives a jamming transition, leading to a colloidal gel. The intermediate overlap regime (c* < c < 40c*) is characterized by a significant compaction of the polyelectrolyte entities prior interdigitation and jamming. (C) 2009 Elsevier Ltd. All rights reserved.