To provide electromagnetic protection for intelligent equipment, advanced electromagnetic wave absorption (EWA) materials are highly desired. To reveal the interaction mechanism of structure and electromagnetic waves, polyaniline (PANI) with various structures, including nanosheets, clusters, and nanofibers, is synthesized via a template-free approach. The self-assembly process of PANI can be regulated by camphor sulfonic acid due to the formation and guidance of charge transfer complexes. A comprehensive analysis of structure, chemical constitution, and electromagnetic characteristics is conducted. Clusters with three-dimensional micro-nano structure exhibit superior microwave absorption, achieving a minimum reflection loss of −52.22 dB at 9.84 GHz with a 3.2 mm thickness and an absorption bandwidth of 6.12 GHz at 2.3 mm thickness. The outstanding EWA performance is attributed to the unique architecture, strong dielectric loss capabilities, and effective impedance matching. Moreover, the fabrication process is cost-effective and scalable, making it conducive to practical applicability.