The invention discloses multi-arm star-network solid polymer electrolyte. The multi-arm star-network solid polymer electrolyte comprises a polymer basic body, a lithium salt and adhesive, wherein the polymer basic body is a multi-arm star-network polymer formed by grafting oxygen-containing and/or sulfur-containing aliphatic ether and/or alcohol molecules onto 1,3,5,7-tetramethyl tetrahydro tetrasiloxane, the highest ion electrical conductivity of the solid polymer electrolyte under the room temperature can reach 1.56*10<-4>S cm<-1>, the mechanical property is good, after the multi-arm star-network solid polymer electrolyte is assembled to form a button-type cell, the button-type cell can be charged and discharged in a wide temperature range (10 to 120 DEG C), and the multi-arm star-network solid polymer electrolyte is particularly suitable for electrochemical energy storage devices such as full-solid lithium ion batteries, lithium-sulfur batteries and super-capacitors at the room temperature and the low temperature.