The invention provides a polyalcohol solid-solid phase-change composite material. The polyalcohol solid-solid phase-change composite material comprises a polyalcohol solid-solid phase-change material and a resin base material, is capable of avoiding the problems of melt flow and osmotic migration, and has wide phase-change temperature range, big phase-change latent heat, and adjustable phase-change temperature and phase-change latent heat. The invention further provides a method for preparing the polyalcohol solid-solid phase-change composite material. The method can be used for preparing the polyalcohol solid-solid phase-change composite materials with all profiles and good constancy and in all sizes. The preparation technology is simple and free from environment pollution. The polyalcohol solid-solid phase-change composite material of the invention has wide application value in the fields, such as the heat protection of aircrafts, the constant-temperature temperature control of precise instruments, meters and electronic devices, heat barrier coating, solar utilization, recovery of industrial residual heat and waste heat, the energy source of electric peak load shifting and valley filling, material, aerospace, textile, electric power, medical instrument, building and the like.