Analytical pyrolysis is a convenient and efficient technique for obtaining structural information on both natural and synthetic polymers through the release of characteristic fragments on rapid thermal degradation. However, commercial pyrolysis systems usually suffer from discrimination of high molecular weight compounds on transfer from the pyrolysis unit to the gas chromatograph. This limits the amount of information that can be gained from pyrolysis experiments. To eliminate this Instrument-based limitation, the technique of non-discriminating pyrolysis based on capacitive discharge heating of a Silcosteel tube filled with the pyrolysed sample was introduced in 2001. This technique has since been applied for the characterization of many different types of samples, including soil, bacteria and airborne particulate matter with minimum or no sample preparation. The approach requires very small amounts of sample material and is fast and simple. A combination of the non-discriminating pyrolysis system with comprehensive two-dimensional gas chromatography/time-of-fllght mass spectrometry (GCxGC/TOF-MS) creates a very powerful tool for the characterization of extremely complex analyte mixtures.