The cloud point curves of a series of oxygen-containing polymers in CO2 were measured to attempt to deduce the effect of oxygen functional groups within a polymer on the polymer/CO2 phase behavior. The addition of an ether oxygen to a hydrocarbon polymer, either in the backbone or the side chain, enhances "CO2-philicity" by providing sites for specific interactions with CO2 as well as by enhancing the entropy of mixing by creating more flexible chains with higher free volume. Ab initio calculations show that both ether and ester oxygens provide very attractive interaction sites for CO2 molecules. The binding energy for an isolated ether oxygen with CO2 is larger in magnitude than that for a carbonyl oxygen/CO2 complex. However, acetate functionalized polymers are more CO2-soluble than polymers with only ether functionalitiespossibly because acetate functional groups contain a total of three binding modes for CO2 interactions, compared with only one for the ether functional group. Experiments clearly indicate that adding a single methylene group as a spacer between a polymer backbone and either an ether or acetate group exhibits a strong deleterious effect on phase behavior. This effect cannot be explained from our ab initio calculations.