Promoting light absorption range of photocatalysts is of great significance to improve solar light‐driven photocatalytic CO2 reduction efficiency. Herein, a new viologen‐based multicomponent heterotrimetallic metal–organic framework (MOF) Cu3Th6(µ3‐O)4(µ3‐OH)4(cpb)12FeIII(CN)66 (IHEP‐14) with an unprecedented (6, 18)‐connected she‐d topology is presented. Upon UV irradiation, this MOF undergoes ligand and iron photoreduction, and a single‐crystal‐to‐single‐crystal transformation to generate persistent radical‐containing MOF Cu3Th6(µ3‐O)4(µ3‐OH)4(cpb•)12FeII(CN)66 (IHEP‐15). This radical‐containing MOF shows excellent stability without fading after at least 2 months in air. Besides extending the photoabsorption to a wider wavelength range covering from 200 to 2,500 nm, the generation of persistent radical in IHEP‐15 also largely enhances its CO2 adsorption capacity by a factor of three due to the strong affinity between π orbital of the radical and the π system of CO2. These attributes endow IHEP‐15 with excellent visible/NIR light‐driven CO2 photoreduction activity, with CO production rates under visible and NIR irradiation of 570.3 and 209.3 µmol h−1 g−1, respectively. Notably, the latter is a record high for NIR‐induced CO production among all MOFs reported so far. A single‐crystal‐to‐single‐crystal (SCSC) transformation of unprecedented (6, 18)‐connected multicomponent MOF IHEP‐14 generates persistent radical‐containing MOF IHEP‐15, accompanied by a marked increase in CO2 sorption and visible/NIR photocatalytic reduction of CO2 to CO with high selectivity. The NIR light‐driven CO production rate of 209.3 µmol h−1 g−1 for IHEP‐15 is recorded high for NIR‐induced CO production among all MOFs reported so far.