Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)₃})₄(μ₄-O)]₂[{(Au{P(m-FPh)₃})₂ (μ-OH)}₂][α-PMo₁₂O₄₀]₂·EtOH (1), [(Au{P(m-FPh)₃})₄(μ₄-O)]₂[α-SiMo₁₂O₄₀]·4H₂O (2), [(Au{P(m-MePh)₃})₄(μ₄-O)]₂[α-SiM₁₂O₄₀] (M = W (3), Mo (4)) and [{(Au {P(p-MePh)₃})₄(μ₄-O)}{(Au{P(p-MePh)₃})₃(μ₃-O)}][α-PW₁₂O₄₀] (5) were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS ³¹P NMR and solution (¹H, ³¹P{¹H}) NMR. Formation of the these gold(I) cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I) cluster cations contained various bridged-oxygen atoms such as μ₄-O, μ₃-O and μ-OH groups.