In this review, we describe the latest advances in synthesis, characterization, and applications of polymer brushes. Synthetic advances towards well-defined polymer brushes, which meet criteria such as: (i) Efficient and fast grafting, (ii) Applicability on a wide range of substrates; and (iii) Precise control of surface initiator concentration and hence, chain density are discussed. On the characterization end advances in methods for the determination of relevant physical parameters such as surface initiator concentration and grafting density are discussed. The impact of these advances specifically in emerging fields of nano- and bio-technology where interfacial properties such as surface energies are controlled to create nanopatterned polymer brushes and their implications in mediating with biological systems is discussed.