Solid-state sodium-ion batteries have attracted significant attention due to their rich resources, high safety, and high energy density. However, the lower ionic conductivity and inferior interfacial contact between solid-state electrolytes (SSEs) and electrodes limit their practical applications. Herein, polyvinylideneuoride-co-hexauoropropylene (PVDF-HFP) membrane is selected and a novel sandwiched composite PVDF-HFP/Na2.5Zr1.95Ce0.05Si2.2P0.8O11.3F0.7/PVDF-HFP (G-NZC0.05SPF0.7-G) SSEs is well designed. The ionic conductivity of Na3Zr2Si2PO12 is enhanced by Ce4+/F− co-doping. The effects of Ce4+ and F− doping on the crystal structure, density, and ionic conductivity for Na3Zr2Si2PO12 are well investigated. The optimal NZC0.05SPF0.7 delivers a high ionic conductivity of 1.39 × 10−3 S cm−1 at 25 ℃. Moreover, the PVDF-HFP membrane can significantly enhance the interface compatibility between NZC0.05SPF0.7 and electrodes. The as-prepared G-NZC0.05SPF0.7-G exhibits a large ionic conductivity of 1.07 × 10−3 S cm−1 at 25 ℃, wide electrochemical stability window up to 4.5 V, high critical current density of 1.2 A cm−2, and stable Na plating/stripping over 600 h at 0.3 A cm−2. The solid-state Na0.67Mn0.47Ni0.33Ti0.2O2/G-NZC0.05SPF0.7-G/Na battery delivers a remarkable cycling stability and rate capability at 25 ℃, indicating that the as-prepared G-NZC0.05SPF0.7-G has a promising application for solid-state SIBs. This study demonstrates an effective strategy to develop advanced solid-state electrolytes for solid-state SIBs.