Belonging to the technical field of building materials, the invention specifically relates to a method for synthesis of tetracalcium aluminoferrite by a sol-gel technology. The raw materials used by the synthesis method include: calcium nitrate tetrahydrate, aluminum nitrate nonahydrate, iron nitrate nonahydrate, citric acid monohydrate, ethylene glycol and water. The specific synthesis steps consist of: dissolving three inorganic salts of certain stoichiometric ratio in deionized water and mixing them uniformly, adding citric acid to prepare a light yellow metal-citric acid chelate solution, then adding ethylene glycol to undergo an esterification reaction, subjecting the obtained sol to aging under complete stirring at 80DEG C so as to obtain sticky wet gel, then further drying it for 24h at 150DEG C to obtain dry gel, and grinding and calcining the dry gel so as to obtain a tetracalcium aluminoferrite monomineral. The tetracalcium aluminoferrite powder prepared by the sol-gel technology has the characteristics of high purity, superfineness, and easy sintering, etc.