We present the first example of surface-initiated polymerization mediated by Lewis pairs for the synthesis of polymer brushes on planar substrates. The method enables the rapid grafting polymerization from the self-assembled monolayer or surface-attached macroinitiators, furnishing linear polymer brushes and bottle-brush brushes. Both homopolyester and block copolyester brushes can be synthesized via this versatile approach. This work not only opens up new opportunities for the application of Lewis pair-mediated polymerization but also enriches the surface-initiated polymerization on different surfaces.
