Self-assembled monolayers (SAMs) and polymer brushes are perhaps the most commonly used surface modification materials. They have driven many of the recent advances in biosensing and (opto)bioelectronic devices. The molecular structure of SAMs includes a headgroup to attach the molecule to the surface, a backbone that provides structure or selforganization, and a tail group that defines surface energy or provides a site for biomolecular binding. For example, silane-based and thiol-based monolayers are the most common SAM motifs utilized on oxide and noble metal substrates, and a variety of functionalized SAMs are routinely patterned for applications in biological assays and for cell attachment surfaces. However, in some cases SAMs suffer from instabilities or excess reactivities in the attachment chemistry which lead to non-uniform modification layers. Polymer brushes provide a higher level customization with a wider range of chemistry, more controllable surface coverage and more uniform layer thickness. Yet, as the spatial resolution requirements and complexity of biointerfaces progress, strategies using traditional polymer brushes face challenges. They lack the versatility to introduce chemical functionalities needed in desired locations along the polymer chain for interfacing between different substrates and different biological media. In summary, there is still a need for new surface modification materials to expand our ability to tune and control a wide variety of interactions at inorganic/bio interfaces that are compatible with high-resolution, highprecision lithographic patterning while maintaining their compatibility with biological systems.