Well-defined poly(methyl methacrylate) (M-n = 3630 g mol(-1), PDI = 1.06) with a primary benzylic bromide prepared using anionic polymerization was successfully transformed into diverse end-functionalities (carboxyl, omega-hydroxy, (omega-methyl-vinyl, omega-trimethylsilane, and omega-glycidyl-ether) via "click" reaction. The bromine end-terminated poly(methyl methacrylate) was first substituted by an azide function and sequentially was reacted with various functional alkynes (propiolic acid, propargyl alcohol, 2-methyl-1-buten-3-yne, propargyl trimethylsilane, and propargyl glycidylether). In all the cases, H-1-NMR, C-13 NMR, FT-IR, and GPC measurements show qualitative and quantitative transformation of the chain-end poly(methyl methacrylate) into the desired functionalities with high conversion (above 99%). (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 1571-1580, 2009