A series of new organic hybrid polyoxovanadate clusters [V₄O₄(μ-OH)₂(acac)₂(Htri)₂] (1, H₃tri = tris(hydroxymethyl) aminomethane, acac = acetylacetone), [V₄O₄(acac)₂(Htri)₂(L)₂] {HL = methanol (2), ethanol (3a and 3b), ethylene glycol (4) and benzyl alcohol (5)}, {V₄O₄(H₂O)₂(tri-acetamide)₂(CH₃COO)₂} (6, H₃tri-acetamide = N-(2-hydroxy-1,1-bis-hydroxymethyl-ethyl)-acetamide), [V₆O₈(μ-OH)₂(Htri)₃]·6H₂O (7) and [V₁₄O₁₈(tri)₂(Htri)₆(HCOO)(CH₃COO)]·2H₂O (8) were prepared by hydro(solvo)thermal methods and characterized structurally. 1 contains [VO(OH)(acac)] and [VO₂(Htri)] units, which are further interconnected via common edges to build a tetravanadyl cluster [V₄O₄(OH)₂(acac)₂(Htri)₂] with the double-deficient cube [V₄O₆]. The tetravanadyl cluster frameworks of 2–5 can be derived from the tetravanadyl cluster of 1 by replacing two –OH groups with two deprotonated organic alcohol ligands, namely, CH₃O⁻ (2), CH₃CH₂O⁻ (3a and 3b), HO(CH₂)₂O⁻ (4) and C₆H₅CH₂O⁻ (5). Interestingly, both 3a and 3b have the same chemical structure, but they exhibit different conformational polymorphisms [denoted as α-type (3a) and β-type (3b)]. Such conformational polymorphisms within the polyoxovanadate clusters incorporating tris(hydroxymethyl)methane derivatives emerged for the first time. 6 displays another tetravanadyl cluster {V₄O₄(H₂O)₂(tri-acetamide)₂(CH₃COO)₂} with a [V₄O₁₆] fragment, where the tri-acetamide unit comes from the amidation reaction of H₃tri and acetic acid and caps the tetrahedral void of the tetravanadyl cluster. The polyoxovanadate cluster of 7 can originate from the Lindqvist-type hexavanadyl cluster [V₆O₁₉] by replacing nine μ-oxides with nine alkoxides of three tri-acetamide³⁻ ligands. 8 exhibits a fully reduced tetradecavanadyl cluster based on the linkage of two heptavanadyl clusters via two O bridges. The magnetic properties of 1–8 show typical antiferromagnetic interactions.