We have developed a novel strategy for decarboxylative radical addition reactions that employs ground-state reduced nicotinamide adenine dinucleotide (NADH) analogues under ambient and open-air conditions, facilitating the efficient formation of Csp3-Csp3 bonds in a variety of substrates. This protocol is distinguished by its operational simplicity, mild reaction conditions, high efficiency, and the use of cost-effective starting materials. Furthermore, experimental studies have provided valuable insights into the reaction mechanism, elucidating the light-independent pathways that promote these transformations.