The carbonization properties of coal-tar pitch were modified by supercritical fluid (SCF) extraction. Pitches extracted with supercritical toluene (SCFE pitch) contained none of the quinoline insoluble (QI) matter responsible for anisotropic structures with small unit sizes. The size of anisotropic structures from SCFE pitches was closely related to the β-resin (toluene insoluble and quinoline soluble fraction) content. Anisotropic structures from blended pitches prepared to have the same β-resin content as SCFE pitches (by blending toluene soluble (TS) and β-resin fractions obtained through a conventional liquid solvent extraction) were smaller. Extraction of the β-resin fraction with supercritical toluene could be interpreted by the co-solvent effects of the TS fraction dissolved in the extract phase. The high concentration of TS fraction in the extract phase enhanced the solubility of the β-resin fraction into this phase. In the raffinate phase, the heavier β-resin components, which are unsuitable for the development of mesophase structures, coagulated and formed unextractable QI matter through reduction in the concentration of the TS fraction. Since the TS concentration in both the phases depends on pressure and the ratio of the amounts of supercritical toluene and pitch, the control of the β-resin content in the SCFE pitches is possible through the adjustment of these two parameters.