The [Mo 5 O 1 3 (OMe) 4 (NO)] 3 - anion either as a mixed Na + /n-Bu 4 N + or Na + /Me 4 N + salt reacts with [Cp*RhCl 2 ] 2 after partial or total elimination of chloride in methanol and, sometimes, subsequent addition of bromide, to form [{Cp*Rh(H 2 O)}Mo 5 O 1 3 (OMe) 4 (NO)] - isolated as a n-Bu 4 N + or Me 4 N + salt, and [{(Cp*Rh) 2 (μ-X)}Mo 5 O 1 3 (OMe) 4 (NO)] (X=Cl or Br). The low-temperature rhodium K-edge extended X-ray absorption fine structure (EXAFS) data for (n-Bu 4 N)[{Cp*Rh(H 2 O)}Mo 5 O 1 3 (OMe) 4 (NO)] and [{(Cp*Rh) 2 (μ-Cl)}Mo 5 O 1 3 (OMe) 4 (NO)] have been fitted by five- and seven-shell models, respectively, and agree well with X-ray crystallographic data for (Me 4 N)[{Cp*Rh(H 2 O)}Mo 5 O 1 3 (OMe) 4 (NO)].2H 2 O and [{(Cp*Rh) 2 (μ-Br)}Mo 5 O 1 3 (OMe) 4 (NO)].CH 2 Cl 2 . These compounds can serve as structural models for the elucidation of the bonding mode of Cp*Rh fragments in other polyoxoanion-supported rhodium(III) complexes. In that way, another compound which could not be analyzed by X-ray diffraction has been identified as an adduct of (n-Bu 4 N) 2 [{Na(MeOH)}Mo 5 O 1 3 (OMe) 4 (NO)] with [{(Cp*Rh) 2 (μ-Cl)}Mo 5 O 1 3 (OMe) 4 (NO)] on the basis of EXAFS data.