Living anionic polymerization of isoprene on a silicon wafer was initiated by treatment of a 1,1-diphenylethylene surface-bound monolayer with n-butyllithium (growth from). The corresponding 1,1 diphenylhexyllithium derivative was used to initiate isoprene polymerization. The poly(isoprenyl)lithium chain ends were functionalized by addition of ethylene oxide to give a hydroxy-terminated polyisoprene brush. The thickness of the polymer brush was 9.5 +/- 1.2 nm by ellipsometry. Grafting living chain ends to the 1,1-diphenylethylene monolayer and surface grafting of telechelic polymers were used for comparison (growth to). The polymer brushes were characterized by XPS, contact angle measurements, ATR-IR, and AFM.