In the field of electromagnetic (EM) wave absorption, intrinsic conductive polymers with conjugated long-chain structures, such as polyaniline (PANI) and polypyrrole (PPy), have gained widespread use due to their remarkable electrical conductivity and loss ability. However, current research in this area is limited to macroscopic descriptions of the absorption properties of these materials and the contribution of various components to the absorption effect. There has been insufficient exploration of the impact mechanisms of polymer aggregation states on the material's absorption performance and mechanism. To address this, a series of flexible PANI sponge absorbers with different molecular weights and aggregation states were prepared. By carefully controlling the crystallinity and other aggregation characteristics of PANI through the adjustment of its preparation conditions, we were able to influence its electrical conductivity and electromagnetic parameters, thereby achieving control over the material's absorption properties. The resulting PANI sponge absorbers exhibited an effective absorption bandwidth (EAB) that covered the entire X-band at a thickness of 3.2 mm. This study comprehensively explores the absorption mechanisms of conductive polymer absorbers, starting from the microstructure of PANI, and providing a more complete theoretical support for the research and promotion of polymer absorbers.