Abstract: | Self‐assembly post‐modification has proven to be an efficient strategy to build higher‐order supramolecular architectures and functional materials. In this study, we successfully realized the construction of a new family of neutral supramolecular polymeric films containing well‐defined metallacycles as the main scaffolds through combination of coordination‐driven self‐assembly with post‐electropolymerization. The obtained neutral polymeric materials were fully characterized by the cyclic voltammogram (CV), SEM, and TEM. The thickness of the films was able to be well regulated by the number of scanning cycles. Moreover, we found that the shape of the metallacycles and the number of triphenylamine moieties played important roles in the formation of the final polymer films. We believe that the introduction of the neutral metallacycles into the final polymer structures not only enriches the library of supramolecular polymeric films but also provides a new platform to study neutral molecule detection, separation, and capture. |