Abstract: C14/EG composite phase change material was prepared by physical adsorption method with n-tetradecane (C14) as phase change material and expanded graphite (EG) as carrier. The micro-morphology, phase change temperature, phase change latent heat and chemical structure of C14/EG composite phase change material were tested by SEM, DSC and FTIR. The quick freeze-thaw cycle tests of phase change energy storage cement-based materials (PCESM) doped (mass ratio to cement) with 0%, 2%, 4% and 6% phase change materials were carried out. The effects of freeze-thaw cycle on the surface damage, mass loss, dynamic modulus loss, compressive strength and pore structure were analyzed, and the deterioration mechanism of PCESM during freeze-thaw cycle was revealed. The experimental results show that C14 can be well adsorbed in the pores of EG, and C14 has good compatibility with EG, and there is no chemical reaction between them. With the increase of C14/EG phase change material content, the porosity increases and the mechanical properties decrease, but the frost resistance increases first and then decreases. The frost resistance of PCESM with 4% C14/EG phase change material is the best.