The present invention relates to a polymer electrolyte of a multi-layer structure and an all solid-state battery comprising the same, wherein the polymer electrolyte can exhibit an effect capable of stably operating in the high voltage positive electrode and in the low voltage negative electrode, when using the polymer solid electrolyte having a multi-layer structure, which includes the first polymer electrolyte layer and the second polymer electrolyte layer of the present invention, and the all solid-state battery containing it is applicable in the battery field of electric vehicle in which high capacity and high-power battery are used.