The sluggish ion transport kinetics and poor interface compatibility are the major challenges for developing high‐performance solid‐state zinc metal batteries. Here, using the densified polyacrylonitrile/silicon dioxide (PAN‐SiO2) nanofiber membrane as a unique multifunctional mediator, a novel mediator‐bridged type of ultrathin (28.6 µm) polymer electrolyte that is rationally designed. The PAN/SiO2 /polyethylene oxide/Zn(OTf)2(PSPZ) polymer electrolyte is demonstrated to significantly enhance multiple kinetics. In addition to superior mechanical properties, the efficient thermal conductive effect endows it with good high‐temperature structural stability. Interestingly, a unique PAN skeleton‐locking‐anion‐enabled fast ion transport mechanism is uncovered to achieve a high Zn2+ migration number (0.71). Moreover, an efficient dendrite‐free Zn deposition guided by a flat dense SEI is demonstrated. In this case, highly reversible Zn metal anodes can be realized in the temperature range extending to −25–80 °C, as well as an impressive 4800 h‐cycle lifespan at the condition of 0.1 mA cm−2. Beyond that, wide‐temperature, high‐rate, durable PSPZ‐based solid‐state Zn/VO2 batteries are also successfully verified. This brand‐new concept of multiple‐kinetics‐enhanced polymer electrolyte design can provide a new perspective for developing all‐climate fast‐charging solid‐state batteries, including but not limited to zinc metal batteries.