Lithium ion conducting polymer electrolytes were prepared by mixing insoluble lithium tetrakis(pentafluorobenzenethiolato) borate (LiTPSB) with poly(vinylidene fluoride) (PVDF) or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Their films were prepared by hot pressing and are investigated for ionic conductivity and thermal properties. LiTPSB is insoluble in PVDF. Ionic conductivity was largely dependent on the salt content for LiTPSB–PVDF composite polymer electrolytes, and exhibited higher ionic conductivity than homogeneous LiTFSI–PVDF based polymer electrolytes. Melting point and crystallinity of PVDF were independent on LiTPSB content, resulting in no difference for melting point and crystallinity between pure PVDF and LiTPSB–PVDF. Ionic conductivity was effectively improved by incorporation of 18-crown-6 or kryptofix222 for LiTPSB–PVDF based polymer electrolytes.