The behavior of pC16TVB, a water-soluble polyelectrolyte-surfactant system shows a change in structure at low pH. Dynamic Light Scattering (DLS), Nuclear Magnetic Resonance (NMR), and Small Angle Neutron Scattering (SANS) are utilized to characterize the transition. SANS experiments suggested that the local structure and cross section of the aggregates do not change with pH. However, the hydrodynamic radius of the aggregate increases with decreasing pH and changes in aggregate flexibility are observed. NMR shows that some of the carboxylate groups of pVB- have been protonated with the addition of HCl, and remain close to the surfactant head groups. NMR also implies intrinsic immobilization of the aggregates at low pH. A simple model of polyelectrolyte chain crossing multiple surfactant spherical micelles has been proposed as the structure of the aggregates at low pH.