In this work, the advanced all solid-state block copolymer electrolytes (SBCPEs) for lithium-ion batteries with double conductive phases, poly(ethylene oxide)- -poly(trimethyl- -((2-(dimethylamino)ethyl methacrylate)-7-propyl)-ammonium bis(trifluoromethanesulfonyl) imide) (PEO- -PDM-dTFSI)/LiTFSI, were fabricated, in which the charged PDM-dTFSI block contained double quaternary ammonium cations and the PEO block was doped with LiTFSI. The disordered (DIS) and ordered lamellae (LAM) phase structures were achieved by adjusting the composition of the block copolymer and the doping ratio . In addition, the presence of the hard PDM-dTFSI block and the formation of the LAM phase structure resulted in a good mechanical strength of the solid PEO- -PDM-dTFSI/LiTFSI electrolyte, and it could maintain a high level of 10 Pa at 100 °C, which was around 10,000 times stronger than that of the PEO/LiTFSI electrolyte. Based on the good mechanical and electrochemical properties, the PEO- -PDM-dTFSI/LiTFSI SBCPE exhibited excellent long-term galvanostatic cycle performance, indicating the strong ability to suppress lithium dendrites.