The preparation of redox-active polymers and the chain-end functionalization with one ruthenium complex was investigated in detail. A series of substituted monomers, i.e., styrenic triarylamines bearing methyl, fluoro, or methoxy substituents, were prepared by a one-pot Hartwig–Buchwald coupling. The nitroxide-mediated polymerization (NMP) was studied by variation of the functional initiators, the monomer-to-initiator ratios, and the solvent. The kinetic analysis of the prototypical methyl-substituted triarylamine shows the controlled polymerization up to 75% conversion, but a considerable decrease of the polymerization rate was observed during the course of the reaction. Both chain-end functionalities of the purified oligomers were subsequently utilized, i.e., the nitroxide to serve as a macroinitiator for an additional NMP step and the chloromethyl group to introduce one ruthenium complex at the chain terminus. The products were analyzed in detail by size-exclusion chromatography, NMR spectroscopy, and ...