AbstractSeveral cellulose derivatives belong to a special class of polymers called hairy‐rod macromolecules which are used to generate well‐defined supramolecular architectures by the Langmuir‐Blodgett (LB) technique. In particular trimethylsilyl cellulose (TMSC) forms monomolecular films on the Langmuir‐trough and is transferred onto hydrophobic substrates with a constant transfer ratio, as it does not undergo chemical changes in the film‐building process. Silylated celluloses was regenerated which represents a convenient method for the generation of homogeneous ultrathin films with hydrophilic surfaces. The adsorption of polymers and dyes as well as biomolecules onto regenerated and modified cellulose LB films have been studied. In addition, chemical reactions, such as cycloaddition, desilylation and crosslinking reactions within single monolayers have been performed.