Ozone‐depleting substances (ODSs) are well known as primary emission from the production and consumption of traditional industrial sectors. Here, we reported the unintentional emission of ODSs from iron and steel plants as a new source, basing on real‐world measurements of flue gases emitted from their major processes. The sintering was found to be the major emission process of ODSs, including chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halons, methyl halide (CH3Cl), methyl chloroform, carbon tetrachloride, methyl bromide and halogenated very short‐lived substances. The median emission factors of CFC‐113, CFC‐115, HCFC‐22, and CH3Cl for typical sintering processes are 1.7, 0.7, 44.5 and 237.0 mg/t, respectively. Quantum chemical calculation figures out that the ODS species are mainly formed in the low efficiency combustion process of halogenated materials. Annual amounts of ODS and CFC‐11‐equivalent emissions were estimated to be 1,785 tons and 78 tons in 2019 over mainland China, respectively. Given these findings, this study provides a new prospective on searching for ODS emission sources, especially unintentional sources such as iron and steel industry and other combustion related activities.