In this study, we disclose for the first time that formate salt can be used as a bifunctional reagent for the synthesis of phenol derivatives and as a CO source for carbonylative cross‐coupling processes using the COware gas reactor under activation free conditions. Key to this success is the in‐situ synthesis of aryl formate via an unprecedented nickel/organophotocatalyst system under blue LED irradiation. This developed system demonstrated high applicability to various aryl iodide substrates for synthesizing phenol derivatives. Moreover, the generated CO could be utilized in a range of carbonylative C‐heteroatom and C−C processes. Notably, commercially available H 13 COONa salt can serve as a bifunctional reagent for both synthesizing phenols and generating 13 CO.