Oppositely charged polymers and surfactants show a complex phase behavior with large regions of solubility and insolubility dependent on the concentrations of the species present. Here, a series of quaternized hydroxyethyl cellulose (cationic) polymers have been characterized by pulsed-gradient spin-echo NMR (PGSE-NMR) and electrophoretic NMR (eNMR) in simple aqueous (D2O) solutions and in combination with the oppositely charged (anionic) surfactant, sodium dodecyl sulfate (SDS). Analysis of the effective charge on the polymer derived from both the eNMR and PGSE-NMR results yields a readily interpretable insight into the polymer behavior; the effective charge on the polymer at infinite dilution shows a linear relationship with the degree of modification. On addition of low concentrations of SDS, typically C-surf < 5 mM, the surfactant interacts with the charged polymers, leading to substantial changes in the dynamics of the system (polymer diffusion, viscosity). At these levels of surfactant addition, there is no macroscopic phase separation. Further, with the absence of an interaction with the parent, the uncharged polymer strongly suggests that the SDS only interacts with the charged moieties present on the functionalized side groups and not the polymer backbone. Ultimately, the charge on the soluble polymer/surfactant complex was found to depend linearly on the level of surfactant binding across a series of polymers with differing levels of modification with the charge becoming effectively zero at the macroscopic phase separation boundary.