Reactive vapor deposition (RVD) is an umbrella term for a suite of techniques used to synthesize uniform, polymeric films directly onto topologically complex surfaces. These techniques are particularly useful for integrating electroactive materials with textile substrates. However, the library of conjugated polymers one can deposit with RVD is minute, and this limits the device architectures and optoelectronic functions one can integrate with textiles. Herein, we use precursors with tailored chemical structures alongside a novel RVD reactor to deposit conjugated polymers previously unattainable using RVD. We outline the parameters used for each deposition to obtain polymer films that conformally coat microtextured surfaces, and we explore the properties of each system for future applications. Finally, we use RVD to construct a proof-of-concept electrode for electrochemical carbon capture and evaluate its performance in redox-active flow cells.