Poly(vinylidene fluoride-hexafluoropropylene)-lanthanum oxide//poly(vinylidene fluoride-hexafluoropropylene)-hexagonal boron nitride (PVH–LaO//PVH-BN) bi-layer separators are developed through a two-step blading approach. La2O3 in the PVH matrix enhances the Li+ conduction by providing extra Li+ conducting pathways owing to the Lewis acid-base interaction of La atoms with the PVH chains, leading to a high lithium-ion transference number of 0.72 and ionic conductivity of 7.5 × 10−4 S cm−1 at room temperature. Moreover, the strong interfacial interaction between h-BN and PVH in the bi-layer separator enhances the thermal and mechanical stabilities of the separator. Batteries based on lithium iron phosphate and the bi-layer separator deliver a discharge capacity of 158 mAh g−1 at 0.5 C after 100 cycles and a rate capacity of 81 mAh g−1 at 10 C after 1500 cycles.