The accelerated arriving of 5G era has brought a new round of intelligent transformation which will completely emancipate smart terminal devices. While the subsequent deleterious effect of electromagnetic wave on electronic devices is increasingly serious, driving the growth of next-generation electromagnetic wave absorbents. As a tactful combination of components and structures, three-dimensional (3D) macroscopic absorbents with fascinating synergy afford exceptional electromagnetic wave absorption, and tremendous efforts have been devoted to this investigation. However, in terms of macroscopic absorbents and their synergistic effect, few reviews are proposed to comb the latest achievements and detailed synergy. This review article focuses on the synergistic effect of macro-architectured absorbents mainly including structure-induced synergy, structure-components synergy, and multiple-components induced synergy. And then the potential construction principles and strategies of macroscopic absorbents are combed. Significantly, the key information for structures and components manipulation including nano-micro design and components regulation is further dissected by critically selected cutting-edge 3D macroscopic absorbents. Moreover, a brief summary of multifunctional electromagnetic wave absorbents (EWAs)-based macroscopic structures is presented. Finally, the development prospects and challenges of these materials are discussed.