High-molecular-weight fragments produced during pyrolysis of both natural and synthetic materials often carry the most significant structural information. Their diagnostic value is usually limited when using commercial pyrolysis devices because of analyte discrimination on transfer from the pyrolysis unit to the GC column. A device enabling pyrolysis in line with GC column was developed to overcome this problem. Pyrolysis is carried out in a segment of deactivated stainless steel tubing. One end of the tubing is connected through a restrictor to a standard GC injector, and the other end is connected to a precolumn followed by a GC column. Pyrolysis is carried out by passing a pulse of electric current from a capacitive discharge power supply through the tubing. Nondiscriminated alkane pattern up to C-58 (limited by the temperature limit of the GC stationary phase) was observed for the pyrolysis of polyethylene. A comparison of conventional pyrolysis with in-column pyrolysis indicates that the range of semivolatile pyrolysis products that can be detected in the pyrograms extends much further toward higher-boiling compounds for the technique proposed. The new approach has also proved very useful in methodical variations of pyrolysis, including thermochemolysis using tetramethylammonium hydroxide.