Multifunctional conductive polymers have been re-designed to achieve both high electronic conductivity and ionic conductivity. In the conventional design of conductive polymers, organic functionalities are introduced via bottom-up synthetic approaches to enhance specific properties by modification of the individual polymers. Unfortunately, the addition of functional groups leads to conflicting effects, limiting their scaled synthesis and broad applications. Here we show a conductive polymer with simple primary building blocks that can be thermally processed to develop hierarchically ordered structures (HOS) with well-defined ordered morphologies. Our approach to constructing permanent HOS in conductive polymers leads to fast ion transport, high ionic and electronic conductivity properties, and mechanical robustness, which are critical for many electrochemical applications.