We developed a new synthetic pathway to novel molybdenum giant cluster compounds, in which pathway the giant cluster solution free from alkali metal or ammonium cations and from residuary species due to the usual preparation (reduction) procedures was used. Through the pathway, we prepared a novel crystalline compound with Ni2+. The crystals exhibited a monoclinic cell with a = 2.9616(5) nm, b = 4.5965(7) nm, c = 2.9641(5) nm, beta = 103.342(15)degrees, and V = 39.263(12) nm(3).