Two kinds of pyridine insoluble fractions (PI) of coal extracts with different solubilities in N-methyl-2-pyrrolidinone (NMP) were characterized in this paper. PI-0 was obtained by the pyridine fractionation of Upper Freeport coal extracts with a CS2/NMP mixed solvent (1: 1 by volume), and its solubility in NMP is 53 wt %. While PI-1, which was obtained by the removal of NMP and tetrabutylammoniurn acetate (TBAA) from a PI-0 solution in NMP containing TBAA, was almost completely soluble in NMP. Solid-state (CNMR)-C-13 spectra indicated that the two PIs have the same chemical structure. The viscoelastic properties and methanol adsorption behaviors of the two PIs were measured. The dynamic viscoelasticities of the two PIs are similar, and the elastic modulus (G') of PI-I is lower before the softening temperature than that of PI-0, suggesting that the macromolecular network of Pl-I is looser compared to that of PI-0. The methanol sorption behaviors of PI-0 and PI-I are also similar, and lines curve-fitted with the Langmuir-Henry equation were in agreement with the experimental data, suggesting that the bulk structure of the two PIs is similar. The methanol sorption for PI-1 is larger than that for PI-0. The constants of the Langmuir-Henry equation obtained by successive fitting for the two PIs indicated that the microporosity of PI-I is larger than that of PI-0. The results obtained here suggested that the dissociation of molecular interactions is responsible for the high solubility of PI-1.