The need for environmentally benign portable energy storage drives research on organic batteries and catalytic systems. These systems are a promising replacement for commonly used energy storage devices that rely on limited resources such as lithium and rare earth metals. The redox-active TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl) fragment is a popular component of organic systems, as its benefits include remarkable electrochemical performance and decent physical properties. TEMPO is also known to be an efficient catalyst for alcohol oxidation, oxygen reduction, and various complex organic reactions. It can be attached to various aliphatic and conductive polymers to form high-loading catalysis systems. The performance and efficiency of TEMPO-containing materials strongly depend on the molecular structure, and thus rational design of such compounds is vital for successful implementation. We discuss synthetic approaches for producing electroactive polymers based on conductive and non-conductive backbones with organic radical substituents, fundamental aspects of electrochemistry of such materials, and their application in energy storage devices, such as batteries, redox-flow cells, and electrocatalytic systems. We compare the performance of the materials with different architectures, providing an overview of diverse charge interactions for hybrid materials, and presenting promising research opportunities for the future of this area.