In this work, hybrid materials containing the fifth sub-group elements, the layered vanadium disulfide-nickel oxide (VS2/NiO), are developed for electromagnetic wave absorption. NiO is uniformly attached to VS2 nanosheets, resulting in a layered microstructure with interlayer voids in the hybrid material. The layered multi-component structure is more to facilitate multiple reflection and leads to a desirable electromagnetic microwave absorption performance. Studies have shown that VS2/NiO hybrid loading is 20% of NiO; the minimum reflection loss value can reach -58.98 dB at 12.32 GHz with thickness of 1.48 mm. When the thickness of the sample is reduced to 1.2 mm, the bandwidth with a RL value less than -10 dB can reach 3.5 GHz. The results show that the remarkable microwave absorption performance can be attributed to satisfactory dielectric and magnetic loss capabilities, good impedance matching, and the special layered structure. This work provides a new option for the design of excellent microwave absorbing materials for practical applications.