omega-Methacryloyl-functionalized poly(tert-butyl acrylate) (PtBA) and poly(n-butyl acrylate) (PnBA) macromonomers with different chain lengths were synthesized by atom transfer radical polymerization (ATRP). The terminal bromine atoms were removed by a chain transfer reaction and esterification. PnBA-g-PtBA graft copolymers and their "inverse" PtBA-g-PnBA counterparts with different chemical compositions were achieved by the "grafting through" approach via ATRP. The reactivity ratios of macromonomer and comonomer are close to unity, enabling the synthesis of graft copolymers with a statistical distribution of side chains. Amphiphilic PnBA-g-PAA graft copolymers and their "inverse" PAA-g-PnBA counterparts were achieved by quantitative hydrolysis of the poly(tert-butyl acrylate) segments to poly(acrylic acid) (PAA).