Heterogeneous electrochemical applications such as energy storage, extractionvia electrolysis, and electrocatalysis is predominantly performed using inorganic or metallic solids as the active electrode due to their robust nature, volumetric density, and electrical conductivity. In several applications such as metallurgy these materials are indispensable due to the harsh processing and operating conditions, but alternatives are being sought in more benign applications such as energy storage and electrocatalysis. Namely, the drawbacks of using inorganic electrodes include the intense extraction, refinement, and synthesis procedures that are highly environmentally destructive, and severe power vs. energy density compromise. Organic electrodes have emerged as appealing alternatives with more abundant feedstock, and better ability to address losses in energy density with increased power of operation. This dissertation covers the importance of understanding fundamental interactions of organic redox-active materials with the electrolyte it operates in, and the influence of its chemical, such as polarizability, and physical, such as backbone flexibility, structural traits on crucial performance metrics such as cycling stability and rate retentions, as well as chemical strategies to incorporate a wider array of redox-active moieties into heterogeneous structures. Understanding and developing redox-active materials using criteria for electrical energy storage elucidates further insights into desired properties for other electrically-driven applications such as (photo)electrocatalysis. Thus this dissertation lays groundwork for expanding the library of moieties and underpinning crucial elements for consideration when designing materials for electroactive applications.