Herein, we report a robust azo-metal-organic framework (MOF), namely, ECUT-15, which can be described as a 10-connected bct net built on trinudear Co-3 subunits. The activated samples of it perform a somewhat breathing behavior. Most importantly, under UV irradiation, this MOP performs outstanding photoswitching behavior toward CO2, giving great variation in the CO2 capture/release performance, for example, 45% under static conditions and 75% under dynamic measurements, as well as instantaneous release of up to 78%.