Solid-state polymer electrolytes have emerged as promising alternatives to liquid electrolytes in lithium-ion batteries, owing to their enhanced safety and thermal stability. Nevertheless, the molecular-level mechanisms governing lithium-ion transport in these materials remain insufficiently understood. In this study, we employ Transition Path Sampling (TPS), a trajectory-based method designed to probe rare events, to investigate lithium-ion transport in three ether-based polymers: C2EO3, C2EO4, and PEO. Our analysis reveals that the connectivity of contiguous polymer segments critically influences the dominant transport mechanism— whether intrachain or interchain hopping. Structural and dynamical correlation analyses further show that efficient ion transport is strongly linked to the solvation shell’s ability to reorganize, particularly through collective motion of Oxygen atoms extending beyond the immediate coordination sphere. To assess the role of nuclear quantum effects in stabilizing solvation environments, we also perform path integral molecular dynamics (PIMD) simulations. These results explain experimentally observed conductivity trends and provide mechanistic insight into lithium-ion transport, offering molecular-level design strategies for the development of next-generation polymer electrolytes with enhanced performance.