One novel octasubstituted trisalkoxotetradecavanadate cluster, [V14O18(tri)(2)(Htri)(6)(HCOO)(2)]center dot 2H(2)O [1; H(3)tri = tris(hydroxymethyl)aminomethane], was revealed by a hydrothermal method. 1 shows a new type of fully reduced trisalkoxotetradecavanadate cluster, incorporating the highest number of H(3)tri ligands, that is constructed by the interconnection of two rare trisalkoxoheptavanadate units via two O bridges. The magnetic and photocurrent response properties were investigated.