The invention discloses a compound concrete admixture with early strength and water reduction functions. The compound concrete admixture is mainly prepared by 10-20 parts by mass of a polycarboxylate water-reducer, 1-5 parts by mass of a surfactant, 5-40 parts by mass of an early strength agent, 2 or less parts by mass of an air entraining agent, and 20-100 parts by mass of water. The preparation method of the compound concrete admixture comprises the following steps: processing a polycarboxylate water-reducer mother liquor to prepare a solution, mixing the polycarboxylate water-reducer solution with the early strength agent, the surfactant, the air entraining agent and water according in proportion, and uniformly stirring. The application of the concrete admixture is realized through the following steps: stirring the concrete admixture and standard sand; taking cement and water, and carrying out low-speed uniform mixing; mixing the above two materials, carrying out low-speed stirring, then carrying out high-speed stirring, intermediately stopping, and then continuously carrying out high-speed stirring; and adding the finally obtained mixture into a mold, and maintaining, wherein the addition of the polycarboxylate water-reducer is not greater than 1% of the amount of a cement mortar. The compound concrete admixture has the advantages of simple preparation method, fast effectiveness, wide application range, low cost and good effect.