AbstractThermoplastic elastomers (TPEs) combine high elasticity with melt processability due to their structural features being based on physical associations rather than chemical crosslinking. Their mechanical properties are governed by the interplay of the different dynamics present in the system (i.e., hard block associations and soft block mobility) combined with their morphology. Irrespective of their exact chemical structure or type of association (crystals, hydrogen bonds, or glassy domains), many soft TPEs show a reduction in toughness at elevated temperatures. In this study, we investigate the high‐temperature mechanical properties of a model series of industrially relevant TPEs via systematically varying composition and molecular weight. The results show an increase in temperature resistance and in large‐strain stress response as chain length increases. We underline the key parameters that influence the mechanical behavior and explain the observed effect of molecular weight on both the temperature‐ and rate‐dependent large‐strain response. A physical network‐based model is presented that can explain the experimental findings assuming an improved network connectivity and extended lifetime of the entangled segments with increasing molecular weight.