(Deuterium‐labeled) CF2H‐ and CFH2‐moieties are of high interest in drug discovery. The high demand for the incorporation of these fluoroalkyl moieties into molecular structures has witnessed significant synthetic progress, particularly in the (deutero)hydrodefluorination of CF3‐containing compounds. However, the controllable replacement of fluorine atoms while maintaining high chemoselectivity remains challenging. Herein, we describe the development of a selective (deutero)hydrodefluorination reaction via electrolysis. The reaction exhibits a remarkable chemoselectivity control, which is enabled by the addition of different organoboron sources. The procedure is operationally simple and scalable, and provides access in one step to high‐value building blocks for application in medicinal chemistry. Furthermore, density functional theory (DFT) calculations have been carried out to investigate the reaction mechanism and to rationalize the chemoselectivity observed. We herein reported an electrochemical selective (deutero)hydrodefluorination reaction of trifluoroacetamides. The reaction which exhibits a remarkable chemoselectivity control and delivers (deuterium‐labeled) CF2H‐ and CFH2‐products in good yields with high level of deuterium incorporation, respectively, is enabled by the addition of different organoboron sources and (deuterated)water as the deuterium or hydrogen source.