PDMS-b-PAA block copolymers were synthesized in a two-step procedure. The first step involves atom transfer radical polymerization (ATRP) of the protected ethoxyethyl acrylate (EEA) monomer initiated with alpha-bromopoly(dimethylsiloxane) (PDMS) ( = 10,000 g/mol) macroinitiator. In the second step the synthesized poly(dimethylsiloxane)-b-poly(ethoxyethyl acrylate) (PDMS-b-PEEA) was deprotected by thermal treatment. The aggregation properties of the copolymers were investigated by atomic force microscopy (AFM) and dynamic light scattering (DLS). The influence of the polymer concentration, the length of the PAA block, the (mixed) solvent composition, and annealing on the size and the shape of the aggregates was evaluated. The results show that the aggregate size and morphology can be successfully controlled by tuning the experimental conditions. These copolymers might possibly be used in the preparation of adhesive materials.