To address the urgent need for efficient and stable electromagnetic wave absorbing materials for electromagnetic interference (EMI) protection, we synthesized Co2FeAl1−xMnx Heusler soft magnetic alloys using a high-energy planetary ball milling method. We comprehensively analyzed their structural characteristics, surface morphology, magnetic properties, and electromagnetic parameters to explore their potential in electromagnetic wave absorption. The results show that incorporating manganese (Mn) significantly changes the alloys' crystal structure, surface morphology, and magnetic properties, greatly enhancing their wave absorption performance. The Mn doping specifically alters the surface morphology, which plays a crucial role in influencing the wave absorption characteristics of the Heusler alloys. When the Mn content increased to 25 %, the sample exhibits superior wave absorption, achieving the maximum reflection loss of −44.83 dB at 13.68 GHz with a thickness of 1.5 mm and an effective absorption bandwidth of 5.52 GHz. With a significant increase in the aspect ratio and noticeable changes in surface morphology, the sample with 75 % Mn content shows exceptional performance with an effective absorption bandwidth of 5.68 GHz, representing the highest effective absorption bandwidth in single-phase Heusler alloys. The Mn doping strategy effectively improves the material's impedance matching by adjusting its permittivity and permeability, facilitating multiple polarization relaxation mechanisms and significantly enhancing the alloys' electromagnetic wave absorption efficiency. Our study provides detailed experimental data for optimizing the electromagnetic wave absorption characteristics of Heusler alloys, verifies their practical application potential, and paves the way for developing new high-performance electromagnetic wave absorbing materials.