Novel star-shaped hard-soft triblock copolymers, 4-arm poly(styrene)-block-poly [poly(ethylene glycol) methyl ethyl methacrylate]-block-poly{x-[(4-cyano-4-biphenyl) oxy] alkyl methacrylate} (4PS-PPEGMA-PMAxLC) (x=3, 10), with different mesogen spacer length are prepared by atom-transfer radical polymerization. The star copolymers comprised three different parts: a hard polystyrene (PS) core to ensure the good mechanical property of the solid-state polymer, and a soft, mobile poly[poly(ethylene glycol) methyl ethyl methacrylate] (PPEGMA) middle sphere responsible for the high ionic conductivity of the solid polyelectrolytes, and a poly{x-[(4-cyano-4-biphenyl)oxy]alkyl methacrylate} with a birefringent mesogens at the end of each arm to tuning the electrolytes morphology. The star-shaped hard-soft block copolymers fusing hard PS core with soft PPEGMA segment can form a flexible and transparent film with dimensional stability. Thermal annealing from the liquid crystalline states allows the cyanobiphenyl mesogens to induce a good assembly of hard and soft blocks, consequently obtaining uniform nanoscale microphase separation morphology, and the longer spacer is more helpful than the shorter one. There the ionic conductivity has been improved greatly by the orderly continuous channel for efficient ion transportation, especially at the elevated temperature. The copolymer 4PS-PPEGMA-PMA10LC shows ionic conductivity value of 1.3 x 10(-4) S cm(-1) (25 degrees C) after annealed from liquid crystal state, which is higher than that of 4PS-PPEGMA electrolyte without mesogen groups. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4341-4350