Construction of materials with multiple interfaces has always been a significant research direction to the high-performance electromagnetic wave (EMW) absorption materials. Here, the composites, consisted of three-dimensional (3D) flower-like NiFe layered double hydroxide (LDH) and regular dodecahedron CoNi-MOF, are synthesized at the first time, and their electromagnetic absorption capacity can be efficaciously improved by altering the proportion of NiFe-LDH (NFL) and CoNi-MOF. Benefiting from the suitable ratio of constituents, at a matching thickness of 2.29 mm, the minimum reflection loss (RLmin) of Z@NFL-2 is −61.87 dB, and the effective absorption bandwidth (EAB, RLmin < −10 dB) is reach up to 6.1 GHz. Especially, Z@NFL-4 can obtain a large EAB of 7.23 GHz (10.77–18 GHz) at a thickness of only 2.06 mm. Amazingly, under the far domain circumstance, the lowest radar cross-section acreage can accomplish −44.72 dB m2. The remarkable EMW absorption performance is mainly attributed to the collaborative effect of abundant electrical-magnetic loss mechanism, and remarkable impedance matching characteristics. Therefore, this work furnishes a fresh idea for exploring the application of LDH-based materials in electromagnetic wave absorption filed.