The NASICON-type solid electrolyte structure of Li1.3Al0.3Ti1.7(PO4)3 (LATP) exhibits good electrochemical performance and thermal stability, and has been promising as a solid electrolyte. Here, a stable goodstability LATP precursor spinning solution was prepared using the sol–gel method for the first time. A linear LATP solid electrolyte with an oriented ordered structure was obtained using improved electrostatic spinning equipment. The sintering process regime of the LATP-ordered construction was determined. The ionic conductivity of the prepared LATP-PEO/LiClO4-PEG composite solid-state electrolyte with an ordered structure was as high as 2.05 × 10-4 S∙cm-1 at room temperature (25 ℃), one order of magnitude higher than the ionic conductivity of the LATP composite solid-state electrolyte reported so far. Organic solid-state electrolytes to protect LATP-ordered structured solid-state electrolytes yield excellent electrochemical stability in lithium-metal batteries.