Re-polymerization reactions are a commonly reported issue on the way to the higher recovery of monomers from lignin. The reactivity of monomers obtained from lignin depolymerization and their contribution to the re-polymerization in supercritical water (SCW) was investigated. Sulfonated Kraft lignin (SKL) was used along with four monomers: vanillin, vanillic acid, vanillyl alcohol and acetovanillone. Indulin Kraft lignin was also employed as the reference to understand the re-polymerization of SKL in SCW. The formation of diarylmethane structures was detected in HSQC spectra of solid residue after the SCW process. Lignin released fragments with free phenolic β-O-4 structures, as well as the monomeric product vanillyl alcohol are involved with the formation of o-o´ and o-p ´ diarylmethane structures. Chemical structure of Kraft lignin and its polymeric product after the SCW process was remarkably similar, as shown by HSQC, indicating that re-polymerization reactions occur through cross-linking polymerization, mainly in their fractions of low molecular weight products.