The NdFe magnetic absorbing materials were prepared by rapid solidification and high-energy ball milling method. The effect of high-energy ball milling on particle morphology, organizational structure and microwave absorbing properties of NdFe magnetic absorbing materials were analyzed with the aid of X-ray diffractometer, scanning electron microscope and vector network analysis. The results show that the Nd2Fe17 and α-Fe phase are refined, the particles become smaller and thinner; the span-ratio of the particles increases along with time during the process of high-energy ball milling; and meanwhile, the frequency of absorbing peak reduces. The absorbing bandwidth broadens as the increase of the time of ball milling, except that of 48h.The minimum reflectance of the powder decreases from -22dB to - 44dB under the circumstances that the time of high energy ball milling reaches 48h and the thickness of the microwave absorbing coating is 1.5mm. But it rebounds to about - 6dB when the time of ball milling reaches 72h.