The combination of two highly non-innocent ligands with a third-row transition metal produces the title complex ion which was crystallised as [Os(Q)₂(bpy)](ClO₄)·C₆H₆ (Q = 4,6-di-tert-butyl-o-iminobenzoquinones, bpy = 2,2^′-bipyridine) and could be structurally characterised to exhibit a tris-chelate situation at the metal with trans-positioned N and cis-positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q˙⁻)Os^III(Q˙⁻) can rationalise the observed S = 1/2 situation with ligand-centred resulting spin. Ligand-based spin is confirmed by DFT (calculated spin populations Q: 1.113; Os: −0.113; bpy: 0.001) and is also apparent from the EPR signal (g₁ 1.981, g₂ 1.955, g₃ 1.803, Δg 0.178, 〈g〉 1.915) which is influenced by the high spin–orbit coupling constant of the osmium centre. The susceptibility measurements reveal antiferromagnetic behaviour. A one-electron oxidation and two one-electron reductions could be monitored spectroelectrochemically (UV-VIS-NIR) and analysed by TD-DFT, in comparison with the results from the ruthenium analogue. The analysis reflects the strong orbital mixing between the metal and the two Q-ligand MOs.