Exploring chemical doping method to improve the electrical conductivity of polymers is still very attractive for researchers. In this work, we report a developed method of doping a polymer semiconductor aided by the coupled reaction that commonly exists in biological systems where a non-spontaneous reaction is driven by a spontaneous reaction. During the doping process, the chemical reaction between the dopant and the polymer is promoted by introducing a thermodynamically favorable reaction via adding additives that are highly reactive to the reduction product of the dopant to form a coupled reaction, thus significantly improving the electrical conductivity of polymers by 3-7 orders. This coupled reaction doping process shows the potential of wide applications in exploring efficient doping systems to prepare functional conducting polymers, which could be a powerful tool for modern organic electronics.