This study describes the electrocatalytic, anticancer, and density functional theory (DFT) studies of a nickel complex, [NiCl(P^N^P)]Cl.EtOH, based on a neutral P^N^P‐type pincer ligand (P^N^P = bis[(2‐diphenylphosphino)ethyl]amine). The ligand was synthesized without time‐consuming and costly amine protection. It was characterized by ¹H NMR, ³¹P NMR, Fourier transform infrared (FT‐IR), UV–vis, and single‐crystal X‐ray diffraction. The complex was isolated as a solvated chloride salt and characterized by FT‐IR, UV–visible, ¹H NMR, ¹³C NMR, and ³¹P NMR spectroscopies as well as single‐crystal X‐ray diffraction and CHN analysis. The ligand and complex crystallized in a monoclinic P2₁/c space group. The molecular structure of the complex contains a four‐coordinated distorted nickel ion with square‐planar geometry. The electrocatalytic hydrogen ion reduction was studied for the nickel complex in an …