Silica microhoneycombs (SMHs) loaded with an ionic liquid (IL) (IL-SMHs) were successfully synthesized by impregnating SMHs with an IL bearing an amino group, trihexyl(tetradecyl)-phosphonium alanate ([P-66614][Ala]). SMHs can incorporate at least 50 wt % [P-66614] [Ala] without its straight channels being clogged as demonstrated by a low pressure drop when He was passed through the material. The IL-SMH containing 50 wt % [P-66614] [Ala] shows a CO2 capacity of similar to 0.26 mmol-CO2.g(-1) in a CO2 33%-N-2 67% atmosphere at 303 K IL-SMHs can be readily regenerated by heating them at 393 K and can be reused at least three times without losing the CO2 absorption ability. IL-SMH can also effectively separate CO2 in a flow system. The length of unused bed was very short (only 19 mm). These results demonstrate the high potential of IL-SMHs to be used for effective CO2 separation in flow systems.