Four simulated distillation (SD) methods with GC-MS, GC, TGA, and VTGA were employed to obtain coal tar distillation curves. Gas chromatography is an expedient technique for the determination of boiling paint range and aromatic ring distribution of coal tar. The SD curve can be obtained by GC-MS technique without calibration mixture. But a capillary column was used in conjunction with a packed precolumn. The boiling point data from GC and GC-MS techniques have good repeatability and identical agreement with true boiling points (TBP). Thermogravimetry analysis (TGA) applied in SD is regarded as a miniature "distillation" without collecting products. Vacuum TGA applied in SD can avoid component decomposition.