The interaction mechanisms of an oppositely charged polyelectrolyte-surfactant pair and dodecanoic (lauric) acid (LA) were experimentally investigated using a combination of nuclear magnetic resonance (NMR) techniques. It is observed that LA significantly affects the interaction between the anionic surfactant sodium dodecylethersulfate (SDES) and the cationic polymer guar modified with grafted hydroxypropyl trimethylammonium chloride (Jaguar C13 BF). Typically, oppositely charged polymers and surfactants interact electrostatically at a certain surfactant concentration known as the critical aggregation concentration (CAC). Once the polymer is neutralized by the surfactant, an insoluble complex (precipitate) is observed (phase separation), and, at concentrations beyond the surfactant critical micellar concentration (CMC'), the system returns to a one phase entity. In a system in which a mixture of SDES-LA is added to the polymer, NMR data show that below the neutralization onset, some of the polymer interacts with SDES, while some of the polymer is adsorbed at the surface of LA solid aggregates present in the system. Furthermore, SDES is found to aggregate in a lamellar-like structure at the polymer side chain prior to the SDES CMC'. Above the SDES (CMC'), LA is solubilized and incorporated at the palisade region of SDES micelles. Analysis of (1)H resonances provided estimated concentrations of all species in the system phases at all stages of interaction.