The chemically cross-linked gel polymer electrolytes supported by the microporous polyethylene membrane were prepared for application in lithium-ion polymer cells. The chemical cross-linking by star-shaped siloxane acrylate allowed to encapsulate an electrolyte solution in the porous membrane and also promote strong interfacial adhesion between the electrodes and the membrane. Lithium-ion polymer cells composed of a mesocarbon microbead anode and a lithium–cobalt oxide cathode were assembled by using in situ chemical cross-linking method, and their charge/discharge cycling performances were evaluated. Effect of the cross-linking agent content on cycling performances of the cells has been investigated.