Cr-Fe₂B composite coatings were prepared on carbon steels by pack-boronizing followed by electro brush-plating. The microstructure and properties of the coatings annealed at different temperatures were studied. The coatings show a gradient structure composed of a Cr-layer and a Fe₂B-layer and have excellent thermal stability, and no new layers and/or transition layers are formed in the coating during annealing up to 1000 °C. The Cr-layer has an amorphous structure and is transformed into nanosized grains when the annealing temperature increases to 700 °C. As the annealing temperature is further increased, the nanograins grow rapidly. The microcracks in the Cr-layer increase sharply after annealing at 550 °C and then decrease significantly with any further increase of the annealing temperature. The pre-deposited Fe₂B-layer prevents the formation of carbon-poor zones in the steel substrate during annealing. It is considered that high-temperature (>700 °C) annealing helps to eliminate coating defects, increase the coating density and obtain better wear resistance and corrosion resistance. Surprisingly, the as-plated and low temperature annealed samples also show good wear resistance and corrosion resistance, which may be related to their amorphous structure and nanocrystalline structure.