Almost all copper in scrap steel is recovered, so research on copper-bearing steel has profound practical significance. The surface enrichment of copper occurs in all copper-bearing steels studied in this paper after being heated at high temperature. In-situ oxidation-induced copper coatings were discovered on the descaled copper-bearing steels after heating at around 1150 °C for 2 h in air. Scattered copper precipitates in or under rust after heating at a lower temperature. A new concept was created using in-situ composites prepared by direct oxidation of matrix, and there was no bonding problem found between the coating and the matrix. The enrichment form of copper in steel is related to the oxidation rate, oxidation time, heating temperature and copper content.