Well-defined star shaped polymers with alpha-Cyclodextrin (alpha-CD) core linking PMMA-block arms were synthesized by atom transfer radical polymerization (ATRP). Gel polymer electrolytes (GPEs) were prepared by encapsulating electrolyte solution of 1 mol L-1 of LiClO4/EC-PC (volume 1:1) into the obtained star shaped polymer host. The ionic conductivity of the GPEs and the cycling characteristics of LiCoO2/GPEs/Graphite cell were studied by electrochemical impedance spectroscopy and charge-discharge testing, respectively. The results indicate that the GPEs have a high ionic conductivity up to 1.63 x 10(-3) S cm(-1) at room temperature and exhibit a high electrochemical stability potential of 4.5 V (vs. Li/Li+). The discharge capacity of LiCoO2/GPEs/Graphite cell is about 98% of its initial discharge capacity after 20 cycles at 0.1 C rate. Discharge capacity of the model cell with GPEs is stable with charge-discharge cycling.