Carbon honeycombs (CHs) are new carbon cellular structures, very promising in many respects, in particular, for high-capacity storage of various materials, especially in gaseous and liquid forms. In this study, we report a strong uptake of carbon dioxide kept inside carbon honeycomb matrices up to temperatures about three times higher as compared with CO2 desorption at ≈ 90 K from flat solid surfaces in vacuum where we conduct our high-energy electron diffraction experiments. Desorption of CO2 from CH matrices upon heating exhibits non-monotone behavior, which is ascribed to carbon dioxide release from CH channels of different sizes. It is shown that modeling of CO2 uptake, storage, and redistribution in the thin CH channels of certain types and orientations upon heating can explain experimental observations. [ABSTRACT FROM AUTHOR]