The thermodegradation of several ethylene-alpha-olefin copolymers, where alpha-olefin was butene-1, hexene-1, octene-1 or 4-methyl-1-pentene, was investigated by the pyrolysis-gas chromatography (Py-GC) technique. The study of the various pyrograms has allowed the discrimination of these polyethylenes (PEs) produced from different catalyst systems and processes. It was shown that the pyrolysis products could be classified into two families depending upon the type of the thermal degradation mechanism. In this way, it was demonstrated that, first, the nature and the amount of the comonomer, and, second, the long chain branching are the two structural features controlling the pyrolysis process. The quantitative ratio of these two families is a promising tool to classify the various polyethylene categories. In addition, a statistical approach was applied to discriminate the different PE families.