Abstract The preparation of enantioenriched diarylmethanol derivatives is described using nickel‐catalyzed electrochemical cross‐couplings between various alkyl/aryl aldehydes and aryl iodides. Performed in an electrochemical cell equipped with an iron anode and a nickel cathode, this electrocatalytic variant led to the scalemic targeted products in the presence of 2,2‐bis((4 R ,5 S )‐4,5‐diphenyl‐4,5‐dihydrooxazol‐2‐yl)acetonitrile ( L2 ), as enantiopure cyano‐bis(oxazoline) ligand. X‐ray structure analysis of a pre‐catalyst, for instance the [Ni (II) ( L2 ) 2 ] complex, with L2 as an anionic bisoxazolinate ligand, confirms the chemical formulation of one nickel surrounded by two ligands. The redox behavior of the new Ni complexes generated in situ was first assessed by cyclic voltammetry showing a redox wave at ca . −1.5 V that can be assigned to the two‐electron reduction of the Ni (II) center to the Ni (0) state. Oxidative addition between the electrogenerated Ni (0) complex and aryl iodide was evidenced. An intense current was observed in presence of a mixture of the two substrates pertaining an electrocatalytic process. Interestingly, we found that the sacrificial iron anode plays a crucial role in the catalytic mechanism.