Highly oriented, layered, and mechanically resilient films of polydopamine (PDA) have been synthesized from the air/water interface. The films show a unique layered structure, as shown by scanning and transmission electron studies (SEM/TEM) and X-ray diffraction analysis (XRD), which resemble that of 2D layered materials. The films exhibit a composition typical of PDA-based materials, as evidenced by X-ray photoelectron spectroscopy (XPS); moreover, the samples present the distinctive resonance modes of PDA-based nanomaterials in Raman and infrared spectroscopy (FTIR) experiments. The presence of highly ordinated 3–4 protomolecule stacking, taking place at the air/water interface, with a unique eumelanin-like supramolecular arrangement is presented. Moreover, the films show superior mechanical resilience with E = 13 ± 4 GPa and H = 0.21 ± 0.03 GPa, as revealed by nanoindentation experiments, making them highly resilient and easily transferable. Finally, the ordering induced by the interface opens many possibilities for further studies, including those regarding the supramolecular structure on PDA due to their similarity to 2D layered materials.