Over the last decade, biology and biotechnology have witnessed an extraordinary development spanning genomics, proteomics, and metabolics. This progress was so rapid and definite that it not only changed the face of modern biology, but indeed altered the way day‐to‐day business is done in biology and related fields. This scientific advancement came with a need for concurrent technological advances. In this context, the ability to interface sophisticated devices with relevant biological microenvironments has emerged as a critical challenge. Already, novel biomaterials are on the horizon that promise to fulfill the rigid criteria of being both biocompatible under the conditions of a versatile range of biological applications and compatible with the increasing demands for miniaturization, integration, and throughput of future device architectures. As currently employed solvent‐based polymer coatings are increasingly reaching their limits, a range of unconventional materials, such as vapor‐based polymer coatings, are discussed as attractive alternatives. One of the main features of vapor‐based polyreactions is their versatility in synthesizing both simple and complex polymers with relative ease and at generally low temperatures. The advantages of the chemical vapor deposition (CVD) technique also include control of the composition and architecture of the resulting materials, high accuracy, solvent‐free environments, excellent adhesion, and the ability to accommodate custom‐tailored surface modifications. For further illustration, selected examples of polymer‐based surface engineering approaches using vapor‐based polyreactions are discussed in this review. For instance, reactive coating technology uses CVD polymerization to deposit a wide range of chemically functionalized polymer coatings on various substrate materials. Its simplicity in providing chemically reactive groups and its applicability to three‐dimensional geometries (e.g. for microfluidics) enables exact tailoring of surface properties and the preparation of biologically relevant microenvironments. CVD‐based reactive coatings are compatible with soft lithographic processes allowing for patterning of proteins, DNA, cytokines, and mammalian cells. Copyright © 2006 Society of Chemical Industry