Heterometallic Anderson wheels of formula [(V^IVO)₂M^II₅(hmp)₁₀Cl₂](ClO₄)₂·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO₄)₂·6H₂O and VCl₃ with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions. Theoretical calculations based on density functional methods reproduce both the sign and strength of the exchange interactions found experimentally, and rationalise the parameters extracted.