The intrinsic limitation of low electrical conductivity of MoSe2 resulted in inferior dielectric properties, which restricts its electromagnetic wave absorption (EMWA) performances. Herein, a bimetallic selenide of MoSe2/CoSe2@N‐doped carbon (NC) composites with hollow core‐branch nanostructures are synthesized via the selenization treatment of MoO3 nanorods coated with ZIF‐67. By adjusting the mass ratio of ZIF‐67 to MoO3, the electromagnetic parameters and morphologies of composites are finely tuned, further ameliorating the impedance matching and EMWA performances. The involvement of NC improves the electronic conductivity of the composites. The synchronously formed heterostructure not only facilitates charge transfer but also leads to the accumulation and uneven distribution of charges, thus enhancing the conductive loss and polarization loss. The hollow core‐branch nanostructure provides abundant conductive networks, heterointerfaces, and voids, significantly enhancing the EMWA property. Density functional theory implies that the heterostructures effectively boost charge transport and change charge distribution, which heightens the conductive loss and polarization loss. As a result, the composites demonstrate a minimum reflection loss value of −53.53 dB at 9.04 GHz, alongside a maximum effective absorption bandwidth of 6.32 GHz. This work offers invaluable insights into novel structural designs for future research and applications.