Variable-temperature FTIR spectra of CO adsorbed on NaCl and KBr films are shown to reveal linkage isomerism, that is, formation of C- and O-bonded adsorption complexes with the same cationic sites. Not all of the sites can be involved in that, only the three- or four-coordinated cations located on kinks, edges, or steps of microcrystals. For NaCl, these adsorption complexes account for the high-frequency (HF) C-O stretching bands at 2175 and 2160 cm(-1). Coresponding LF bands of O-bonded CO were found at 2115 and 2124 cm(-1). In the spectrum of KBr, the HF band is poorly resolved, and only one LF band can be clearly seen, near 2124 cm(-1). The value of the isomerization enthalpy for complexes that account for the bands at 2160 and 2124 cm(-1) of CO adsorbed on NaCl, estimated from the experiment, is 4.0 +/- 0.2 kJ/mol. Quantum mechanical calculations by DFT methods applied to NaCl model clusters interacting with the CO molecule confirm the existence of two potential wells with adsorption and isomerization energies close to the experimentally measured values, and enable us to estimate the height of the potential barrier between the two adsorption states.