In this work, we designed a novel polyvinylidene fluoride (PVDF)@DNA solid polymer electrolyte, wherein DNA, as a plasticizer-like additive, reduced the crystallinity of the solid polymer electrolyte and improved its ionic conductivity. At the same time, due to its Lewis acid effect, DNA promotes the dissociation of lithium salts when interacting with lithium salt anions and can also fix the anions, creating more free lithium ions in the electrolyte and thus improving its ionic conductivity. However, owing to hydrogen bonding between DNA and PVDF, excess DNA occupies the lone pairs of electrons of the fluorine atoms on the PVDF molecular chains, affecting the conduction of lithium ions and the conductivity of the solid electrolyte. Hence, in this study, we investigated the effects of adding different DNA amounts to solid polymer electrolytes. The results show that 1% DNA addition resulted in the best improvement in the electrochemical performance of the electrolyte, demonstrating a high ionic conductivity of 3.74 × 10–5 S/cm (25 °C). The initial capacity reached 120 mAh/g; moreover, after 500 cycles, the all-solid-state batteries exhibited a capacity retention of approximately 71%, showing an outstanding cycling performance.