Polyurethane (PU) and its numerous fine-tuned derivatives are widely employed as CO2scavengers thanks to (1) physisorption and (2) functionalization of the PU backbone with otherCO2 sorbents. In the present work, it has been unraveled why PU cannot exhibit CO2chemisorption, despite possessing the nitrogen docking sites and exhibiting strong electrostaticsorbent-sorbate interactions. Furthermore, a few types of spatial separation of the active sorptionsites have been proposed to unleash the chemisorption functionality of PU. By comparing variousstructural modifications of PU by using the in-silico methodology, we have identified that CO2chemisorption by PU takes place in the case of implementing methyl and ethyl fragments betweenthe oxygen and nitrogen atoms of PU. Herewith, the introduction of the ethyl moiety even makesCO2 chemisorption energetically favorable relative to physisorption. The reported specificprogress on materials design represents an obvious practical value for chemical engineersdeveloping inexpensive CO2 scavengers.