Recent joint mass spectrometric and IR photodissociation studies have provided proof on the existence of octa-coordinated ionic lanthanide-carbonyl complexes under those extreme gaseous conditions. In contrast, in older literature concerning cryogenic studies of neutral Ln(CO)xspecies, the highest coordination was assigned to hexa-coordinated Ln(CO)6molecules. The present study aims to clarify the above controversy using matrix isolation spectroscopy and DFT calculations. In order to ensure the maximum possible coordination, the Ln(CO)xcomplexes were synthesized in neat CO cryogenic matrices at 10 K and were investigated by infrared and UV-visible spectroscopy. The formed complexes were identified on the basis of the characteristic CO stretching frequencies of the ground-state molecules predicted by DFT calculations. Our joint experimental–theoretical analysis confirmed the preference of octa-coordinated Ln(CO)8complexes in cryogenic neat CO matrices.