A new ATRP initiator, 11-(2-bromoisobutyrate)-undecyl-1-phosphonic acid, has been synthesized and grafted as a film on a mechanically polished stainless steel (ASI304) substrate. Molecular integrity of the grafted initiator in the film, alkyl chain ordering, wettability were determined by X-ray photoelectron spectroscopy, infrared, and water contact angles. Polystyrene, poly(methyl methacrylate) and diblock copolymer (polystyrene-b-poly(methyl methacrylate)) brushes have been grafted from the flat stainless steel surfaces through surface-initiated atom transfer radical polymerization (ATRP) and characterized to check the effectiveness of the new initiator for future uses in surface-initiated ATRP.