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Understanding how adsorbates influence polaron behavior is of fundamental importance in describing the catalytic properties of TiO 2 . Carboxylic acids adsorb readily at TiO 2 surfaces, yet their influence on polaronic states is unknown. Using UV photoemission spectroscopy (UPS), two-photon photoemission spectroscopy (2PPE), and density functional theory (DFT) we show that dissociative adsorption of formic and acetic acids has profound, yet different, effects on the surface density, crystal field, and photoexcitation of polarons in rutile TiO 2 (110). We also show that these variations are governed by the contrasting electrostatic properties of the acids, which impacts the extent of polaron-adsorbate coupling. The density of polarons in the surface region increases more in formate-terminated TiO 2 (110) relative to acetate. Consequently, increased coupling gives rise to new photoexcitation channels via states 3.83 eV above the Fermi level. The onset of this process is 3.45 eV, likely adding to the catalytic photoyield.