The fabrication of multilayer assemblies from polymeric compounds is an important tool for precise control of film architecture on the nanoscale. In this report, a general, novel approach for the preparation of well-defined polymeric multilayers is described. To achieve this, sulfonyl-azide group containing polymers are first generated and deposited as thin films onto solid (organic) substrates. Upon thermal activation, the system crosslinks and binds to the substrate via C–H bond insertion. Through step-and-repeat procedures, multilayer assemblies are then generated where all the individual layers are linked to each other. As the assembly process does not require any specific molecular interactions, the described process represents a general strategy to generate tailor-made multilayer surface coatings with wide range of film thickness and composition.