Gel polymer electrolytes (GPEs) based on hyperbranched poly (ether urethane) (PHEU) were prepared from the reaction of the hyperbranched polyether (PHEMO) with different dusocyanates in liquid electrolyte. The ionic conductivities and transference number of the GPEs were investigated by altemating current (AC) impedance and multi-potential steps. It is found that the ionic conductivities of GPEs were influenced by dusocyanate structure, lithium salt concentration and addition amount of liquid electrolyte. Sample PUM-0.5M-80% originated from 4, 4-diphenylmethane dusocyanate (MDI) as the hard segment shows the highest ionic conductivity of 2.41 x10-3 S·cm-1 at ambient temperature. The lithium ion transference number is 0.7. Inaddition, small molecules of liquid electrolyte were perfectly entrapped by polymer matrix, and liquid leakage in lithium ion battery was avoided.