Abstract: The occurrence forms of organic nitrogen in Xianfeng lignite (XL), Xiaolongtan lignite (XLT) and Shengli lignite (SL) as well as their extraction residues were characterized by X-ray photoelectron spectroscopy (XPS). The results show that the content distributions of organic nitrogen in the three extraction residues are different, but all are mainly dominated by pyrrole nitrogen. The NaOH-catalyzed supercritical methanolysis of lignite extraction residues at 300℃ was then investigated, which indicates that the yields of petroleum ether soluble portions from supercritical methanolysis of extraction residues derived from XL, XLT and SL are 46.0%, 43.8%, and 47.6% (mass ratio), respectively. The characterization of nitrogen-containing compounds (NCCs) in petroleum ether soluble portions by Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS) indicates that NCCs are mainly composed of N₁, N₁O₁-N₁O₅, N₂, N₂O₁-N₂O₄, N₃O₂ and N₅O₂-N₅O₄ class species. The molecular structural characteristics of NCCs were speculated according to the distributions of double bond equivalent values and carbon numbers, which shows that most of NCCs contain oxygen-functional groups like hydroxyl and carboxyl groups, and the nitrogen atoms are mainly present in aromatic structures (mainly 1-3 aromatic rings) in the forms of pyrrolic, pyridinic and amino groups. The cleavage of C-O bridged bonds in lignite is an important pathway for producing NCCs.