Abstract: By refining scientific research results, the preparation of a nickel complex with electrocatalytic hydrogen evolution activity was introduced into undergraduate comprehensive experimental teaching. An ionic nickel(II) complex (Ni(bpy)3Ni(mnt)2) was prepared using 2,2'-bipyridine (bpy), 1,2-dicyano-1,2'-dithiolene (mnt) and nickel chloride as raw materials. The complex was characterized by single crystal X-ray diffraction, infrared spectroscopy, electrospray ionization mass spectrometry, and ultraviolet-visible spectroscopy. Its electrocatalytic hydrogen evolution performance in both organic and aqueous phases was investigated. The results show that in a phosphate buffer solution at an applied voltage of −1.15 V, the complex produces 0.386 mmol of hydrogen over 4 h, with a turnover number (TON) of 2922.13, and exhibits good stability. This experimental project features simple synthetic procedures, combines cutting-edge and comprehensive aspects, covers numerous knowledge points and experimental technologies, and helps foster students’ awareness of green and low-carbon development while enhancing their innovation ability and scientific research skills.