The invention relates to a preparation technique for thermal spraying nano-microcrystalline enamel. The process comprises the steps that 1, an enamel glaze block is prepared, specifically, a raw material prepared according to a formula and mixed uniformly is fed into a high-temperature furnace to be melted sufficiently at the temperature of 1300-1500 DEG C and is subjected to water quenching to obtain the homogeneous enamel melted glaze block; 2, thermal spraying powder is prepared, specifically, the melted glaze block is smashed and ground, enamel pre-grinding powder is obtained, 5-30% of nano-silica is added into the pre-grinding powder, mixing granulation is carried out, and the nano-microcrystalline enamel powder for thermal spraying is obtained; and 3, thermal spraying and overall crystallization are conducted, specifically, the enamel powder is uniformly sprayed on the surface of a workpiece through a thermal spraying gun, and the powder is melted and liquefied in the process of being spayed out from the spraying gun and is cooled and solidified after being sprayed on the surface of the workpiece; the obtained enamel layer is a multiphase composite material with nanocrystallines, microlite and glass being interwoven together. The enamel layer has the characteristics of being good in corrosion resistance, high in density, good in toughness, high in impact resistance, capable of being formed at a time and low in manufacturing cost.