Designing hydrogels with self-assembled or self-organized structures has become an attractive field of research because these hydrogels usually have robust functions and promising applications, such as in artificial tissues and optical sensors. However, the self-organized structures developed in synthetic hydrogels via molecular self-assembly are generally limited to the submicrometer or micrometer level, which is far from the related scale achieved in biological tissues. Therefore, it is desirable to create macroscopically ordered structures in hydrogels; these structures should greatly improve the material's functionalities, such as their optical properties. In this review, we generally introduce our recent studies on the synthesis of hydrogels with macroscopic-scale liquid crystal structures based on the self-assembly of a semi-rigid polyanion, poly(2,2 0 -disulfonyl-4,4 0 -benzidine terephthalamide) (PBDT). Upon electrostatic interaction with multivalent cations or polycations, PBDT molecules form semi-rigid complexes or mesoscopic bundles that further self-assemble into macroscopic organized structures and are frozen by the subsequent gelation process. We have developed physical hydrogels with centimeter-scale anisotropic structures, polycationic hydrogels with millimeter-scale cylindrically symmetric structures and plate gels with cubic-packed concentric domains. This work should contribute to the development of macroscopic self-organized structures in hydrogel materials with specific functions.