Linear alkylbenzene sulfonate (NaLAS) surfactant is often combined with polycarboxylate polymers in detergent formulations. However, the behavior of these aqueous surfactant-polymer systems in the absence of an added electrolyte is unreported. This work investigates the behavior of such systems using polarized light microscopy, small-angle X-ray scattering (SAXS), centrifugation, and 2H NMR techniques. A phase diagram at 50 °C is reported for 0-50 wt % NaLAS concentrations and 0-10 wt % polycarboxylate concentrations. The NaLAS-water system is micellar at concentrations <35 wt %, and a 2-phase micellar-lamellar system is seen at higher NaLAS levels, consistent with that reported by previous studies. As polymers are added at low surfactant concentrations (∼10 to 20 wt % NaLAS), a second optically isotropic phase is formed; this is thought to be a polymer-rich phase. Further addition of polycarboxylate leads to the formation of a lamellar phase. At high surfactant concentrations (>20 wt % NaLAS), the addition of a polymer induces a second lamellar phase. These observed behaviors are thought to arise as a result of depletion flocculation and salting-out effects. The observed lamellar phases adopt colloidal multilamellar vesicle (MLV) structures, and the average MLV radii were estimated using 2H NMR by probing the diffusion and anisotropy of D2O within the bilayers of the vesicles. The NMR results show that as the polymer concentration was increased from 0 to 10 wt %, an increase in the average multilamellar vesicle size from ∼200 to ∼500 nm was observed. This increase in the calculated average MLV radius likely results from depletion flocculation-induced MLV fusion.