Due to the process complexity of the high‐carbon high‐manganese steel (HMnS) in casting and arc welding, this article propose the coaxial powder‐feeding laser cladding (LC) of HMnS coating using self‐developed HMnS powders. Firstly, high‐carbon HMnS coatings are prepared on the 16Mn substrate using coaxial powder‐feeding LC technology. It has a single austenite phase, without large defects such as pores and cracks. Then, ultrasonic shock peening is used to harden the HMnS coating, and the mechanical properties such as microhardness, impact toughness, wear and tensile properties are measured, which prove that HMnS coating has excellent working hardening, plasticity, toughness, and wear resistance properties. Finally, transmission electron microscopy is used to investigate the coupling effects such as dislocations, multiple twinning, and stacking faults on the HMnS coating after tensile fracture (true strain 39.2%). The deformation strengthening mechanism based on the dynamic Hall–Petch effect is revealed. The research results provide a new method for the preparation of high‐carbon HMnS coatings, and a new idea for expanding the application of high‐carbon HMnS.