AbstractWe developed the dynamic assembly of the hydrogen‐bonded multilayers of (poly(N‐vinylpyrrolidone/poly(methacrylic acid)) (PVPON/PMAA)) and compared their properties to the static multilayers. We found that dynamic multilayers, wherein a planar substrate is shaken during polymer adsorption, leads to a 15‐time faster deposition of the planar coatings. The thicknesses and roughness of the dynamic coatings were found to be ⁓30% larger than those of static (no shaking) multilayer films as measured by spectroscopic ellipsometry and atomic force microscopy. We examined the film growth, mechanical properties, wettability, hydration, and pH stability of the planar static and dynamic multilayers and demonstrated that these properties were insignificantly affected by the assembly mode. Both static and dynamic coatings produced microporous films when exposed to pH = 5.9, close to the film critical dissolution pH = 6. We discovered that during the release of the multilayer films into a solution to produce free‐standing films either as planar membranes or multilayer capsule shells, the molecular chain rearrangements result in the decreased roughness for both static and dynamic multilayers and lead to a decreased thickness of the dynamic multilayers. Our findings can help develop a rapid synthesis of thicker nanostructured polymer coatings for sensing and controlled delivery applications.