In this work, spherical flower-shaped composite carbonyl iron powder@MnO2 (CIP@MnO2) with CIP as the core and ultrathin MnO2 nanosheets as the shell was successfully prepared by a simple redox reaction to improve oxidation resistance and electromagnetic wave absorption properties. The microwave-absorbing properties of CIP@MnO2 composites with different filling ratios (mass fractions of 20%, 40%, and 60% after mixing with paraffin) were tested and analyzed. The experimental results show that compared with pure CIP, the CIP@MnO2 composites have smaller minimum reflection loss and a wider effective absorption bandwidth than CIP (RL < −20 dB). The sample filled with 40 wt% has the best comprehensive performance, the minimum reflection loss is −63.87 dB at 6.32 GHz, and the effective absorption bandwidth (RL < −20 dB) reaches 7.28 GHz in the range of 5.92 GHz–9.28 GHz and 11.2 GHz–15.12 GHz, which covers most C and X bands. Such excellent microwave absorption performance of the spherical flower-like CIP@MnO2 composites is attributed to the combined effect of multiple beneficial components and the electromagnetic attenuation ability generated by the special spherical flower-like structure. Furthermore, this spherical flower-like core–shell shape aids in the creation of discontinuous networks, which improve microwave incidence dispersion, polarize more interfacial charges, and allow electromagnetic wave absorption. In theory, this research could lead to a simple and efficient process for producing spherical flower-shaped CIP@MnO2 composites with high absorption, a wide band, and oxidation resistance for a wide range of applications.