Attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) was used to identify the structures formed during the adsorption of sodium polyacrylate (NaPA) on charged TiO2 particles and to determine the subsequent interaction of the adsorbed polymer structure with cationic and anionic surfactants. The nature of the polymer structure was deduced from the adsorbed amount in tandem with the information obtained from monitoring the change in the relative intensity of the COO- and COOH infrared bands. In particular, it is found that the relative number of COO- and COOH groups on the polymer backbone for the adsorbed state differs from that of the same polymer in solution. This difference is due to a shift in the population of COO-/COOH groups on the polymer backbone that arises when the COO- groups bind to positively charged sites on the surface. A change in the number COO-/COOH groups on the polymer is thus related to a change in the bound fraction of polymer. It is shown that the initial NaPA approaching the bare surface adopts a flat conformation with high bound fraction. Once the bare sites on the surface are covered, the accommodation of additional polymer on the surface requires the existing adsorbed layer to adopt a conformation with a lower bound fraction. When the adsorbed NaPA is probed with a solution containing the anionic surfactant sodium dodecyl sulfate (SDS), the SDS competes for surface sites and displaces some of the bound NaPA segments from the surface, giving rise to an polymer layer adsorbed with an even lower bound fraction. In contrast, addition of a solution containing the cationic surfactant cetyltrimethylammonium bromide (CTAB) results in the binding of the surfactant directly to the free COO- sites on the adsorbed polymer backbone. Confirmation of a direct interaction of the CTAB headgroup with the free COO- groups of the polymer is provided by intensity changes in the headgroup IR bands of the CTAB.