Reactions between a variety of vanadium(II) and iron(II) starting materials in tetrahydrofuran (thf) solution afforded di-, tri-, and tetra-nuclear complexes containing thf or N,N,N′,N′-tetramethylethylenediamine (tmen) as ligands. Most products were ionic and contained the two metals in different structural units, cation or anion. Trinuclear clusters formulated as [V3−xFexCl₅(tmen)₃][BPh₄](x=0–3) were obtained and characterised by C, H, N and metal analyses, ¹H NMR, Mössbauer, and positive ion FAB and electrospray mass spectroscopies, and magnetic moment measurements in solution. We characterised fully by low-temperature single-crystal X-ray diffraction analysis the mixed-metal triangulo-complex salt [V₂Fe(μ-Cl)₃(μ₃-Cl)₂(tmen)₃][BPh₄].