The insoluble organic matter (IOM) of the Orgueil meteorite contains deuterium-rich radicals detectable by Electron Paramagnetic Resonance (EPR) techniques (Gourier et al., 2008). However the structure of these deuterium carriers remains poorly constrained. In this work, their electronic structure is deduced from the measurement of the spin states S by transient nutation in pulsed-EPR. It is shown that these deuterium-rich radicals are dominated by biradicaloids (species with S = 0 ground state and thermally accessible S = 1 state) and biradicals (species with S = 1 ground state) representing ~61% and ~31% of the radicals in the IOM of Orgueil, respectively, while single radicals (S = 1/2) contribute only to ~8%. This is definitely different from mature terrestrial IOMs, which are known to contain almost exclusively S = 1/2 radicals. A structural model is proposed, whereby the occurrence of dominant biradicaloids and biradicals is the direct consequence of the structure of the IOM, made of a network of small aromatic moieties linked by branched and short aliphatic units. This implies that the formation of stable biradicaloids and biradicals by C–H breaking and their deuterium enrichment are produced after the formation of the IOM in the primitive solar system. These results reinforce the idea that the formation of the IOM and the deuterium-rich hotspots are the product of ion chemistry in the solar disk.