The unique applications of porous metal-organic framework (MOF) liquids with permanent porosity and fluidity have attracted significant attention. However, fabrication of porous MOF liquids remains challenging because of the easy intermolecular self-filling of the cavity or the rapid settlement of porous hosts in hindered solvents that cannot enter their pores. Herein, we report a facile strategy for the fabrication of a MOF liquid (Im-UiO-PL) by surface ionization of an imidazolium-functionalized framework with a sterically hindered poly(ethylene glycol) sulfonate (PEGS) canopy. The Im-UiO-PL obtained in this way has a CO2 adsorption approximately 14 times larger than that of pure PEGS. Distinct from a porous MOF solid counterpart, the stored CO2 in Im-UiO-PL can be slowly released and efficiently utilized to synthesize cyclic carbonates in the atmosphere. This is the first example of the use of a porous MOF liquid as a CO2 storage material for catalysis. It offers a new method for the fabrication of unique porous liquid MOFs with functional behaviors in various fields of gas adsorption and catalysis.