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An appropriate amount of toluene 2, 4-diisocyante ( TDI ) was added into polyether( [ ( CH2 CH2 O )13 CH2 O ] n )/Li salt electrolyte to form a cross-linked network, with improving the film processability and thermal stability. The relation between the structure and ionic conductive properties of the cross-lined polyether electrolytes was investigated by means of Fourier transform infra-red spectroscopy (FTIR), differential scanning calorimetry ( DSC ), mechanical property and AC impedance spectroscopy. The electrolytes system is found to have two glass transitions , and it is found that the two Tgs increase with increasing salt concentration . At the same Li .salt concentration, the conductivity of cross-linked polyether/ LiN ( CF3 SO2 )2 complex system is higher than that of LiClO4 . At EO/ Li = 25:1 ( mol ratio ), the former conductivity changes with temperature, while the later coincids with Arrhenius formula (σ= Ae Ea/RT). The cross-linked polyether/ LiN( CF3 SO2 )2 electrolyte exhibits the maximum σ = 10-4.75 S/cm at 30 ℃ .