Abstract Type II porous liquids are demonstrated to be promise porous materials. However, the category of porous hosts is very limited. Here, a porous host metal–organic polyhedra (MOP‐18) is reported to construct type II porous liquids. MOP‐18 is dissolved into 15‐crown‐5 as an individual cage (5 nm). Both the molecular dynamics simulations and experimental gravimetric CO 2 solubility test indicate that the inner cavity of MOP‐18 in porous liquids is unoccupied by 15‐crown‐5 and is accessible to CO 2 . Thus, the prepared porous liquids show enhanced gas solubility. Furthermore, the prepared porous liquid is encapsulated into graphene oxide (GO) nanoslits to form a GO‐supported porous liquid membrane (GO‐SPLM). Owing to the empty cavity of MOP‐18 unit cages in porous liquids that reduces the gas diffusion barrier, GO‐SPLM significantly enhances the permeability of gas.