Diverse phases of Fe 2 O 3 manifest distinct physical and chemical attributes. Herein, Fe 2 O 3 and Fe 2 O 3 @C dodecahedrons with the yolk-shell structure were prepared by controllable pyrolysis of MIL-88 MOFs with different processes. The corresponding pyrolytic stages in air were proposed, followed closely via a similar self-oxidation/reduction procedure in the N 2 atmosphere. In terms of microwave absorption performance, the hollow α-Fe 2 O 3 @C nanocomposites with the yolk-shell structure could facilitate the dielectric loss, and the interfaces between α-Fe 2 O 3 and C promote the dissipation of an electromagnetic wave, which improve electromagnetic attenuation capability and enrich the loss mechanism of Fe 2 O 3 collaboratively. Due to its carbon-coated hollow structure, αγ-Fe 2 O 3 @C nanocomposites calcinated at 400 °C exhibit the best ability for electromagnetic energy conversion. The device has a matching thickness of 2.25 mm, an effective absorption bandwidth of 11.2 to 15.64 GHz, and a total width of 4.44 GHz. Its highest reflection loss (RL) is −52 dB at 8.6 GHz (X band). In the range of −80 < θ < 80, the maximum radar cross section (RCS) reduction of α-Fe 2 O 3 @C is greater than 20 dB m 2 . A great deal of attention has been paid to theoretical simulations of RCS because of its reasonable composition and low-cost features. This work breaks ground for fabricating a MIL-88-derived electromagnetic wave absorber via the enlightenment of RCS simulations.