The novel hollow-magnetite (HFO)/MXene nanohybrids with coral-like structure were successfully prepared via templating and electrostatic self-assembly techniques for electromagnetic (EM) wave adsorption application. The unique coral-like structure of the prepared HFO/MXene hybrids was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). When mass ratio of HFO to MXene is 2:1, the maximum effective absorption bandwidth (EABmax) of HFO/MXene hybrids is able to reach 5.36 GHz. Moreover, when mass ratio of HFO to MXene is 1:1, the minimum reflection loss (RLmin) even achieves −42.48 dB with a thickness of 3.1 mm. The excellent EM absorption performance of HFO/MXene hybrids is mainly due to the ideal impedance matching and synergistic effect of magnetic loss and dielectric loss caused by unique coral-like structure. This work provides unexplored areas in the design of the spatial structure of MXene for microwave absorption.