The evolving field of photocatalysis requires the development of new functional materials, particularly those suitable for large-scale commercial systems. One particularly promising approach is the creation of hybrid organic/inorganic materials. Despite being extensively studied, materials such as polydopamine (PDA) and titanium oxide continue to show significant promise for use in such applications. Nitrogen-doped titanium oxide and free-standing PDA films obtained at the air/water interface are particularly interesting. This study introduces a straightforward and reproducible approach for synthesizing a novel class of large-scale multilayer nanocomposites. The method involves the alternate layering of high-quality materials at the air/water interface combined with precise atomic layer deposition techniques, resulting in a gradient nitrogen doping of titanium oxide layers with exceptionally sharp oxide/polymer interfaces. The analysis confirmed the presence of nitrogen in the interstitial and substitutional sites of the TiO2 lattice while maintaining the 2D-like structure of the PDA films. These chemical and structural characteristics translate into a reduction of the band gap by over 0.63 eV and an increase in the photogenerated current by over 60% compared with pure amorphous TiO2. Furthermore, the nanocomposites demonstrate excellent stability during the 1 h continuous photocurrent generation test.