Outstanding electroactive properties of certain crystallographic phases of poly(vinylidene fluoride) (PVDF) bring much attention to its melting and crystallisation behaviour for tailoring crystallographic nature. In the past

the focus was put on operating conditions in terms of melting and crystallisation kinetics

whereas a deeper understanding of the molecular structure–property relationship of PVDF is sparsely addressed. This study is the first survey to investigate systematically the structure–property relationship by clarifying the question

how molecular weight distribution affects thermal–caloric properties and hence polymorphous phase behaviour. It is shown that molecular weight strongly influences electroactive phase formation and plays a key role in phase design.