It is of significance to construct continuous multiphase percolation channels with fast lithium-ion pathway in hybrid solid electrolytes. 3D ceramic nanostructure frameworks have attracted great attention in this field. Herein, the three-dimensional perovskite Li_0.33La_0.557TiO₃ nanotubes framework (3D-LLTO-NT) is fabricated via a facile coaxial electro-spinning process followed by a calcination process at 800 °C. The hybrid polymer electrolyte of 3D-LLTO-NT framework and poly (ethylene carbonate) (3D-LLTO-NT@PEC) shows improved ionic conductivity of 1.73 × 10⁻⁴ S cm⁻¹ at ambient temperature, higher lithium-ion transference number (t_Li+) of 0.78 and electrochemical stability window up to 5.0 V vs Li/Li⁺. The all-solid-state cell of LiFePO₄/3D-LLTO-NT@PEC/Li delivers a high specific capacity of 140.2 mAh g⁻¹ at 0.1 C at ambient temperature. This outstanding performance is attributed to the 3D ceramic nanotubes frameworks which provide fast lithium ion transfer pathway and stable interfaces.