Two novel heterometallic complexes [Cd(NH3)(6)][{VO-(O-2)(2)(OH)}(2){mu-Cd(NH3)(4)}] (2) and [{VO(O-2)(2)(Im)}(2){mu-Cu(Im)(4)}] (3) (Im = imidazole) containing peroxidovanadium complexes as metalloligands were prepared and characterized by spectral methods. X-ray single-crystal analysis revealed the presence of unique trinuclear complexes in the crystal structures of 2 and 3. The structure of 2 contains an anionic complex, whose two {VO(O-2)(2)(OH)}(2-) ions are interconnected by a {mu-Cd(NH3)(4)}(2+) group. Compound 3 is a trinuclear neutral complex comprising two {VO(O-2)(2)(Im)}(-) ions and a single bridging {mu-Cu(Im)(4)}(2+) group. The bonding via an equatorial OH- ligand in 2 and via a doubly bonded apical oxygen atom in 3 represents coordination modes previously unobserved for diperoxidovanadium complexes. Compared with complex 2, density functional theory studies reported decreased Cu-mu-O bond orders and increased mu-O-V bond orders in 3, in accordance with the expected Jahn-Teller distortion of the latter complex.