Posttransfer modification of preformed Langmuir-Blodgett films of poly(tert-butyl methacrylate) and poly(tert-butyl acrylate) by gaseous hydrochloric acid yields films with layered architecture of poly(methacrylic acid) and poly(acrylic acid), respectively. X-ray reflectivity and infrared spectroscopy confirm monolayer by monolayer transfer of the source polymers and their transformation to acid multilayer assemblies with retention of low surface roughnesses. The incorporation of cross-linking groups into the system offers the possibility for further chemical modification to produce ultrathin films of model networks desirable for bioadsorption studies and as hydrophilic spacing layers for tethered membranes.