This paper proposes a strategy to fabricate surface activated polyethylene (PE)-supported gel polymer electrolyte (GPE) with high ion transport ability, excellent electrolyte retention and mechanical properties to stabilize lithium (Li)-metal anodes. The inert outer and inner pore surface activation of polyethylene is demonstrated by coating an ultrathin zirconium oxide nanocrystal (ZrO2)/polyhedral oligomeric silsesquioxane (POSS) composite layer through a simple layer by layer (LBL) assembly method prior to the in situ polymerization. It is found that the activation layer may improve the Li+ ion transference number and induce the formation of GPE with a gradient structure by the interaction with the initiator system, giving rise to higher ion transport ability of final GPE. On the other hand, the GPE using the activated PE separator as support improves the Li/electrolyte interfacial stability during storage and repeated lithium plating/stripping cycling. A stable voltage profile with cycling for more than 800 h in a Li/Li symmetric cell was obtained by using surface activated PE-supported GPE. When it is assembled into the cells with metallic lithium anodes and lithium cobalt oxide (LiCoO2) cathodes, the cells show excellent rate capability and cycling performance, as well as effective dendrite inhibition.