In situ Fourier transform infrared (FTIR) spectroscopy was employed to characterize the adsorption behavior (as a function of pressure or time) and surface species of CO2 molecules on pure, phosphated, and phosphonated CaO. Carbonate and bicarbonate species were found to form on the pure oxide, whereas on the phosphated and phosphonated oxide samples the carbonate species were found to substitute favorably some of the OH(-) and PO4(3-) groups thereon exposed, respectively. Before and after carbonation, the test samples were further examined by in situ FTIR spectroscopy of adsorbed pyridine species, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Then they were in situ acidified by exposure to a wet atmosphere of HCl vapor at 673 K for 10 min and re-examined similarly to reveal the influence of CO2 adsorption on the chemical and morphological consequences of acidification. The results obtained show the carbonate substitution of PO4(3-) groups to enhance agglomeration of the otherwise fine, longitudinal material particles into much bulkier ones and to render the otherwise more stable phosphonate groups less stable to acid treatment than the phosphate groups. Moreover, the bulky particle agglomerates of the carbonated test samples were detectably eroded following the acid treatment.