Abstract: Coplanar torsional conformation plays a key role in shaping the unique characteristics and functions of conjugated organic macromolecules. It is still an elusive task, however, to control the coplanar yet rigid conformation of conjugated polymers for materials performance. We aim to establish general synthetic methodology and comprehensive structure-property correlations of rigid coplanar pi-systems, through synergistic approaches combining chemical synthesis, process engineering, and materials characterization. In order to achieve this goal, we have designed and implemented multiple chemical strategies, including the incorporation of non-covalent bridging bonds, the use of dynamic covalent reactions, and the employment of highly efficient annulation reactions. Efforts were also made to solve the major challenges associated with low solubility of rigid coplanar macromolecular materials for characterization and processing. Unique optical, electronic and mechanical properties of these new materials are investigated and optimized for advanced applications.