NASICON-type fast ion conductor powders Li1.3Al0.3Ti1.7(PO4)(3) (LATP) are prepared by spray-drying and sintering processes confirmed by XRD and SEM analyses. Novel poly(vinylidene fluoride-hexafluoropylene) (P (VDF-HFP))-based composite polymer electrolytes (CPEs) doped with various amounts of LATP particles are fabricated via classical inverse-phase method. As a result, the as-prepared CPE-5 membrane can present excellent physicochemical properties when the doped amount is maintained at 5% vs. polymer matrix, in which the interfacial impedance value can rapidly stabilize at 472 Omega and the thermal decomposition temperature can be up to 430 degrees C, respectively. In particularly, the ionic conductivity can be as high as 3.943 mS cm(-1) at 25 degrees C. In addition, the assembled LiCoO2/CPE-5/Li coin cell can deliver a discharge specific capacity of 145.4 mAh g(-1) at 1.0 C with 96.93% capacity retention ratio after 25 cycles. These outstanding properties can promote the CPE-5 to be a candidate electrolyte to improve the performance of lithium ion batteries.