In this work, a new class of single Li-ion conducting polyelectrolytes (SLICPs) were skillfully synthesized from highly delocalized lithium tetrazolate, polyethylene glycols (PEGs) and diisocyanates. The chemical composition of SLICPs was confirmed by FT-IR, NMR and XPS, and the physical and electrochemical properties were investigated with XRD, SEM, DSC, TG, EIS, LSV, etc. The results showed that the related properties could be tailored using various diisocyanates and PEGs, and the SLICPs comprising PEG1000 exhibited higher ionic conductivities and Li+ transference number. It was noted that the conductivity of SLICP prepared from isophorone diisocyanate, lithium tetrazolate and PEG 1000 (IPULi-1000) could be close to 1 × 10−4 S cm−1 at 80 °C without uptake of any organic solvents. Besides, the polymer electrolytes could endure an oxidation potential up to 4.2 V (vs. Li+/Li), and the stable cycle (more than 200 cycles for Li/Li symmetric cell at 30 °C) indicated that the developed SLICPs were compatible with lithium electrode. Hence, the developed SLICPs were promising solid polymer electrolytes materials for Lithium batteries.