Poly(arylene ether) and polyamide based single ion conducting polymer electrolytes were comparatively studied. The flexible poly(arylene ether) based backbone is apt to form a dense and uniform blend film in comparison with the rigid polyamide based backbone. The ether segments in poly(arylene ether) facilitates the lithium ion conduction in the polymer matrix. Gel-type LiPHFE blend polymer electrolyte is able to construct compatible and stable electrochemical interface.