Adsorption of carboxymethyl cellulose (CMC) in aqueous solution onto a titania nanoparticle film has been studied using in situ attenuated total reflectance infrared spectroscopy (ATR-IR). CMC was adsorbed onto the positively charged titania surface in neutral, partially charged, and fully charged state. The response of the adsorbed polyelectrolyte layer was monitored upon changing the electrolyte pH and ionic strength. The degree of dissociation of the CMC increased upon adsorption onto the titania surface and changed with the surface coverage. Ionic strength change was observed to influence the degree of dissociation of the adsorbed CMC similar as when in solution. No significant peak shifts were observed in the spectrum of the adsorbed CMC during adsorption or in response to changing solution conditions; therefore, inner-sphere complexation between the carboxyl groups and the titania could not be confirmed. The effect of ion identity on the adsorption process was studied using soft and hard cations and mono- and divalent cations. The presence of a divalent counterion was observed to cause changes in the carboxymethyl vibrations, which can be related to formation of intra- or interchain linkages.