Reliable experimental IR and theoretical approaches, both investigating CO adsorption on NaY faujasites, are supporting that CO capture occurs through the completion of the vacant coordination of Na+ cations located in the accessible SII sites. As a result, carbonyl adsorbed species are formed by the capture of one, two or three CO molecules and are experimentally discernable by their respective IR positions that are down-shifted by an average 11-12 cm−1 value for each captured CO molecule. DFT analysis is proposed for comparison and reproduces well the observed experimental shift of the νCO positions of the different polycarbonyls of interest. In addition, the effect of Si or Al composition surrounding the SII Na+ cation is investigated and results suggest that polycarbonyls that are formed might be in connection with the acidic strength of the cationic sites. This combined study completes and improves the understanding of the complex issue of CO adsorption at 80 K widely used as a model to explain how physical adsorption takes place in NaY faujasites working as an efficient industrial adsorbent in gas separation or gas purification processes.