The CoCrFeNiMn high-entropy alloys were treated by powder-pack boriding to improve their surface hardness and wear resistance. The variation of boriding layer thickness with time and temperature was studied. Then, the frequency factor D0and diffusion activation energy Q of element B in HEA are calculated to be 9.15 × 10−5m2/s and 206.93 kJ/mol, respectively. The diffusion behavior of elements in the boronizing process was investigated and shows that the boride layer forms with the metal atoms diffusing outward and the diffusion layer forms with the B atoms diffusing inward by the Pt-labeling method. In addition, the surface microhardness of CoCrFeNiMn HEA was significantly improved to 23.8 ± 1.4 Gpa, and the friction coefficient was reduced from 0.86 to 0.48~0.61.