Hard–soft–hard triblock copolymers based on poly(ethylene oxide) (PEO), poly(2-naphthyl glycidyl ether)-block-poly[2-(2-(2-methoxyethoxy)ethoxy)ethyl glycidyl ether]-block-poly(2-naphthyl glycidyl ether)s (PNG-PTG-PNGs), were synthesized by sequential ring-opening polymerization of 2-(2-(2-methoxyethoxy)ethoxy)ethyl glycidyl ether and 2-naphthyl glycidyl ether using a bidirectional initiator catalyzed by a phosphazene base. Four PNG-PTG-PNGs had different block compositions (fwt,PNG = 9.2–28.6 wt %), controlled molecular weights (Mn = 23.9–30.9 kDa), and narrow dispersities (Đ = 1.11–1.14). Most of the PNG-PTG-PNG electrolytes had much higher Li+ conductivities than that of a PEO electrolyte (6.54 × 10–7 S cm–1) at room temperature. Eespecially, the Li+ conductivity of PNG18-PTG107-PNG18 electrolyte (9.5 × 10–5 S cm–1 for fwt,PNG = 28.6 wt %) was comparable to one of a PTG electrolyte (1.11 × 10–4 S cm–1). The Li+ conductivities of PNG-PTG-PNG electrolytes were closely correlated to efficient Li+ transpor...