The hydrothermal reactions of V2O5, H2Ca2O4, Ni(NO3)(2), ethylenediamine(en) or 1,2-diaminopropane(enMe) and water yield layered vanadium oxides with interlayer metal coordination complexes [Ni(en)(2)](0.5)[V3O7] (1) and [Ni(enMe)(2)](0.5)[H(2)enMe](0.5)[V6O14] (2). 1 crystallizes in an orthorhombic system with space group Pbcn and cell parameters a = 16.617(3) Angstrom, b = 6.6329(9) Angstrom, and c = 17.138(4) Angstrom. 2 crystallizes in a triclinic system with space group P (1) over bar and cell parameters a = 6.6698(7) Angstrom, b = 10.8679(11) Angstrom, and c = 13.6097(13) Angstrom. Both compounds are inorganic/organic compositions and consist of layered mixed-valence vanadium oxides with interlayers {Ni(en)(2)}(2+) or {Ni(enMe)}(2+) and H(2)enMe(2+). in the structure of 1, a novel arrangement of vanadium and oxygen atoms of {V3O7}(-) was found different from that in its isomer [Zn(en)(2)][V6O14]. In 2, both {Ni(enMe)}(2+) and H(2)enMe(2+) serving as unusual pillars between {V6O14}(2-) layers were observed. Their infrared characters and thermal stabilities were also given.