The mobile phase in supercritical fluid chromatography (SFC) is a substance raised above its critical temperature and pressure which exhibits greater solvating properties together with reduced viscosities and higher diffusivities than its liquid state. The eluting power of supercritical mobile phase can be varied widely by controlling pressure, temperature and composition. Thus, SFC offers many advantages over high‐performance liquid chromatography (HPLC) in the characterization of polymers and oligomers. SFC of polymeric substances has been operated so far in the three modes of chromatography: adsorption chromatography for the separation of oligomer homologs, size‐exclusion chromatography (SEC) for the determination of molecular weight distribution, and adsorption chromatography at critical conditions for the characterization of functionality type distribution. The combination of SFC with supercritical fluid extraction (SFE) is useful for the analysis of polymer additives, such as stabilizers and plasticizers, in an industrial polymer material. SFC is compatible with most conventional HPLC and gas chromatography (GC) detectors, and can also be interfaced with infrared (IR) spectroscopy and mass spectrometry (MS), etc.