The adsorption of carbon monoxide on the LaB 6(1 0 0) and LaB 6(1 1 1) surfaces was studied experimentally with the techniques of reflection absorption infrared spectroscopy and X-ray photoelectron spectroscopy. The interaction of CO with the two surfaces was also studied with density functional theory. Both surfaces adsorb CO molecularly at low temperatures but in markedly different forms. On the LaB 6(1 1 1) surface CO initially adsorbs at 90 K in a form that yields a CO stretching mode at 1502–1512 cm −1. With gentle annealing to 120 K, the CO switches to a bonding environment characterized by multiple CO stretch values from 1980 to 2080 cm −1, assigned to one, two, or three CO molecules terminally bonded to the B atoms of a triangular B 3 unit at the (1 1 1) surface. In contrast, on the LaB 6(1 0 0) surface only a single CO stretch is observed at 2094 cm −1, which is assigned to an atop CO molecule bonded to a La atom. The maximum intensity of the CO stretch vibration on the (1 0 0) surface is higher than on the (1 1 1) surface by a factor of 5. This difference is related to the different orientations of the CO molecules on the two surfaces and to reduced screening of the CO dynamic dipole moment on the (1 0 0) surface, where the bonding occurs further from the surface plane. On LaB 6(1 0 0), XPS measurements indicate that CO dissociates on the surface at temperatures above 400 K.