The invention relates to a composite modified hydration heat regulation material. Starch is firstly reacted with an acid catalyst and a crosslinking agent, and then a product is reacted with alkenyl succinic anhydride to obtain the composite modified hydration heat regulation material, wherein the amount of the acid catalyst is 5 to 25 % of the mass of the starch, the amount of the crosslinking agent is 1 to 5% of the mass of the starch, and the amount of the alkenyl succinic anhydride is 10 to 30% of the mass of the starch. The invention also provides a preparation method and application of the hydration heat regulation material. The regulation material is prepared by a starch crosslinking reaction, and has a spatial network structure, and high resistance to acid and alkali and high shear resistance, the peak value of the hydration heat release rate can be effectively reduced, and the compressive strength of concrete is improved; meanwhile, by introducing a polar acetyl functional group, the polarity characteristic of the hydration heat regulation material is improved, the number of intermolecular hydrogen bonds is reduced, and the freeze-thaw property of the material is improved; and the modified hydration heat regulation material has the advantages of reducing the surface tension of a cement pore solution, generating independent closed bubbles, also playing an air entraining role of a three-dimensional network structure, improving the freeze-thaw property of concrete, and being favorable for the practical application of the hydration heat regulation material.