Detailed knowledge on chain mobility in polymers is of fundamental interest in order to understand their mechanical properties. As a specific example, the melting behavior of semi-crystalline polyethylene can be studied by thermal analysis and NMR spectroscopy. In ultra high molecular weight polyethylene (UHMW-PE) crystallised via different routes, i.e., directly during polymerisation, from solution, or from the melt, and melted under different protocols, different melting processes involving detachment of stems from the crystals and cluster melting can be distinguished. Melting by the consecutive detachment of chain stems from the crystal substrate ultimately results in a melt state where chain dynamics for entanglement formation are much more restricted. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA.