In order to investigate effects of exchangeable metallic species on solvent extraction of lignites and provide a reference for demineralization of lignites rich in alkali and alkaline earth metals (AAEMs), Xiaolongtan lignite (XL) was subjected to acid treatments by hydrochloric acid or ammonium acetate solution separately. Exchangeable metallic species, including Ca2+ and Na+, were subsequently loaded into the partly demineralized sample by ion-exchanged method. Raw coal and all the treated samples were then extracted by organic solvents with different polarities. The variations of functional groups during extraction process and the separated portions were characterized by multiple techniques. The results show that exchangeable metallic species could reduce extract yields of XL. Low extract yields could be attributed to the enhanced compactness of coal structure and inefficient interactions between coal and solvent molecules. The demineralized treatment, especially when hydrochloric acid was used, could obviously increase the extract yields with pyridine or tetrahydrofuran by releasing ionic cross-links and the inherent hydrogen bonds in lignites. On the contrary, ammonium acetate treatment contributes slightly to increasing extract yields. According to the decreasing ratio of extract yields, it could be verified that the intensity of hydrogen bond (OH)-H-center dot center dot center dot is stronger than that of (NH)-H-center dot center dot center dot formed between coal and solvents. Gas chromatograph/mass spectrometer detection indicates that the compositions of extracts strongly depend on the solvent types and the amount of AAEMs. In conclusion, existence of AAEMs significantly influences the dissolving capacity of lignites in organic solvents. (C) 2015 Elsevier B.V. All rights reserved.