Composite polymer electrolytes exhibit promising potential for wearable electronic devices due to their superior electrochemical performance and flexibility. The incorporation of functional fillers can optimize material properties through multiple mechanisms. The PCL-IL&TMP&KL-Zn electrolyte was synthesized by compositing ionic liquid-terminated polycaprolactone (PCL-IL) with zinc-intercalated kaolinite (KL-Zn). The results revealed that the electrolyte incorporating KL-Zn filler demonstrated significantly enhanced overall performance compared to other electrolytes. The electrolyte membrane displays excellent flexibility, high ionic conductivity, and a high zinc ion transference number, suggesting that KL-Zn not only constructs zinc ion transport channels but also enhances ion transport selectivity, thereby significantly boosting zinc ion transport efficiency. The α-MnO2/Zn full battery assembled with this electrolyte retained 91.09% capacity after 200 cycles at 0.5 C, coupled with a coulombic efficiency of 99.6%, demonstrating outstanding cycling stability. Crucially, the raw materials used for this electrolyte such as PCL and kaolinite are low-cost and widely available, exhibiting potentially practical application in flexible battery and intelligent packaging.