The hydrogen transfer reaction is one of the key chemical processes of coal conversion. The elucidation of the hydrogen transfer mechanism is essential for rational control of the properties and distribution of products. This paper is focused on the hydrogen transfer mechanism of lignite modification in a subcritical D2O-CO system. Using Soxhlet extraction, isotope ratio mass spectrometry, H-1 nuclear magnetic resonance, and pyrolysis-gas chromatography-mass spectrometry (Py-GCMS), the deuterium transfer routes in deuterated products and their representative structures were studied. The existing form of deuterium in deuterated products was also proposed. The results showed that the subcritical D2O-CO system can generate active deuterium, which combines with the free radical fragments resulting from coal pyrolysis to form three kinds of deuterated products: n-hexane solute (NS-D), benzene solute (BS-D), and tetrahydrofuran solute (TS-D). Deuterium in the three solutes migrates in the order TS-D -> BS-D -> NS-D. It was observed that the active deuterium is not transferred to the beta sites of the solutes but rather to their ar, alpha,2, alpha, and gamma sites. Py-GCMS detection results showed that the solutes mainly consist of six representative structures, that is, monocyclic and polycyclic aromatics, alkenes, alkanes, alcohols, and esters. In the modification process, deuterium is incorporated into the monocyclic aromatic structures in the aliphatic side chains first and then in the aromatic ring. For the polycyclic aromatic structures, the active deuterium enters the side chain first and then the aromatic ring having that side chain. A small amount of active deuterium can be incorporated into the alkene and alkane structures directly. However, it mainly transfers to such structures indirectly through thermal cracking of deuterium-containing macromolecular aromatic structures. Active deuterium reduces oxygen in the oxygen-containing structures to form OD or DHO, yet it cannot easily enter the aliphatic and aromatic structures linked to the oxygen-containing structures. This research provides a new perspective for the study of hydrogen transfer routes and can serve as a reference for discussing the molecular mechanisms involved in various coal conversion processes.