The adsorption of CO on reduced, rutile TiO2(110) is investigated using IR reflection-absorption spectroscopy and temperature-programmed desorption. Experiments using s- and p-polarized IR light incident along the  and [11̅0] azimuths give detailed information on the adsorption geometry of the CO as a function of the CO coverage, θCO. The results indicate that for θCO ≤ 1 ML, CO adsorbs oriented perpendicular to the surface at Ti5c sites. For 1 < θCO ≤ 1.5 ML, the bonding geometry of the CO adsorbed at Ti5c sites is unchanged, whereas the additional CO molecules adsorb at Ob sites parallel to the surface and parallel to the [11̅0] azimuth. The results do not support previous suggestions that CO at Ti5c sites tilt ∼20° from normal at high coverages. The results demonstrate the utility of polarization-resolved infrared reflection-absorption spectroscopy for elucidating adsorption geometries on dielectric substrates.