2D materials hold promising potential for novel gas separation. However, a lack of in‐plane pores and the randomly stacked interplane channels of these membranes still hinder their separation performance. In this work, ferrocene based‐MOFs (Zr‐Fc MOF) nanosheets, which contain abundant of in‐plane micropores, are synthesized as porous supports to fabricate Zr‐Fc MOF supported ionic liquid membrane (Zr‐Fc‐SILM) for highly efficient CO2 separation. The micropores of Zr‐Fc MOF nanosheets not only provide extra paths for CO2 transportation, and thus increase its permeance up to 145.15 GPU, but also endow the Zr‐Fc‐SILM with high selectivity (216.9) of CO2/N2 through the nanoconfinement effect, which is almost ten times higher than common porous polymer SILM. Furthermore, based on the photothermal‐responsive properties of Zr‐Fc MOF, the performance is further enhanced (35%) by light irradiation through a photothermal heating process. This provides a brand new way to design light facilitating gas separation membranes.