Macromolecular brushes with a gradient of side-chain spacing along the backbone havebeen synthesized by the “grafting from” approach using atom transfer radical polymerization. Amacroinitiator was prepared in two steps, first by conducting a gradient copolymerization of MMA andHEMA-TMS followed by transformation of the resulting poly(MMA-grad-HEMA-TMS) to poly(MMA-grad-BPEM). The gradient composition of the macroinitiator was a forced gradient formed by continuousfeeding of HEMA-TMS during MMA polymerization. The gradient structure was characterized bymonitoring monomer conversion (GC) and molecular weight evolution (GPC) during copolymerization.AFM measurements demonstrated the characteristic anisotropy of the molecular structure by resolvingindividual brush molecules with a bulky head and a thin tail.