Material technology platforms able to modulate the communication with cells at the interface of biomaterials are being increasingly experimented on. Progress in the fabrication of supports is simultaneously introducing new surface modification strategies aimed at turning these supports from passive to active components in engineered preparations. Among these platforms, polymer brushes are arising not only as coatings determining the physical and (bio)chemical surface properties of biomaterials, but also as smart linkers between surfaces and biological cues. Their peculiar properties, especially when brushes are synthesized by “grafting-from” methods, enable closer mimicking of the complex and heterogeneous biological microenvironments. Inspired by the growing interest in this field of materials science, we summarize here the most prominent and recent advances in the synthesis of grafted-from polymer brush surfaces to modulate the response of adhering cells.