AbstractSelenium is one of the most volatile toxic elements in coal, and its emissions must be strictly controlled. Chemical looping combustion (CLC) is a clean and efficient technology for coal. Herein, the iron‐based oxygen carrier (OC) was used as an adsorbent to study the migration and emissions of selenium during the CLC of coal. Due to the oxidation and adsorption of selenium by iron‐based OC, most of the selenium was retained in OC or distributed in the CO2 stream. The proportion of gaseous selenium released into the atmosphere was less than 10%—significantly lower than that from the traditional combustion process of coal, which had a value of 91.79%. The presence of OC increased the distribution phase of selenium, promoted the conversion of gaseous selenium to solid selenium, and reduced selenium emissions in flue gas. During CLC of coal, the fuel reactor (FR) temperature and the number of OC re‐oxidation cycles played an important role in the emissions and retention of selenium. The increasing FR temperature increased the gaseous selenium in the CO2 stream, reduced the particulate selenium absorbed by OC, and reduced the selenium emissions in the atmosphere. After 10 continuous CLC cycles, the selenium concentration in OC increased from 0.889 to 8.20 mg kg−1. The continuous cycling of CLC could realize the enrichment of selenium from coal to OC. Furthermore, the migration and transformation mechanism of selenium during CLC was deduced by experiments and thermodynamic simulation. This research provides a suitable reference for reducing selenium emissions and developing CLC technology.