AbstractThe thermal decomposition of normal alkanes and linear poly(α‐olefins) was found to occur predominately by random scissions, followed by volatilization into an open system. To show these processes the fragment distribution from high molecular weight linear polyethylene (fragments to C55),n‐alkanes, polypropylene, and polyisobutylene (fragments to C60) are reported and discussed in depth. Based on the results, a mechanism of random scissions followed by volatilization is postulated for polyethylene andn‐alkanes as well as for polyisobutylene and polypropylene. Polystyrene is shown not to follow the same mechanism, for little evidence for fragments above trimers was found. In addition, temperature rise–time measurements at the pyrolyzer probe are reported and e