Comprehensive Summary Polyvinylidene fluoride (PVDF), the second largest produced fluoropolymer, exhibits outstanding chemical, physical, electroactive and electrochemical properties and is involved in many High‐Tech applications. This review reports recent novelties in synthesis, characterization, processes and applications. Recent preparation studies deal with the effect of the additives (originally, fluorinated surfactants as PFOA, then hydrocarbon ones, whereas nowadays no surfactants are used), process (greener aqueous emulsion of suspension and abatements in process) to obtain high molar mass and crystallinity, better mechanical, ferro‐, piezo‐ and triboelectric properties. The influence of the reaction temperature vs the Head‐to‐Head defects in PVDF chaining is highlighted. Recent studies on the reversible deactivation radical polymerization of VDF are also reported. Regarding per‐and polyfluoroalkyl substance (PFAS) concerns, PVDF is not water soluble, not toxic, not bioaccumulative and does not cross the lipidic human membrane. Applications encompass electronics, healthcare, automotive, aerospace, energy ( e.g ., storage including lithium‐metal technologies), industrial processing, driving the market growth. The current challenges are its recycling, reuse strategies or degradation without releasing PFAS to reduce environmental impact. Though PVDF market undergoes severe issues caused by PFAS restrictions, it has a CAGR of 7.2% driving the demand for efficient materials in increasing areas globally. Thus, PVDF continues being indispensable across many sectors. Key Products Commercially available PVDF: Kynar® (Arkema), Solef® (Syensqo), Inoflar® (Gujarat Fluorochemicals), KF® Polymer (Kureha), 3F®T‐1 or T‐2 (Shanghai 3F), Tecaflon® (Ensinger), Ftor‐Plast (Halopolymer).
B. Ameduri (Tue,) studied this question.
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