We describe the formation of pseudo-star copolymers via incorporation of an isocyanate-bearing monomer, dimethyl meta-isopropenyl benzyl isocyanate (TMI) into a homopolymer of butyl acrylate (BA) using a one-pot, two-step synthesis. The resultant product maintains the functionality of the isocyanate moiety, which is used to attach poly(ethylene glycol) methyl ether onto the copolymeric chain under benign reaction conditions. The resultant pseudo-star copolymers were isolated and their self-assembly in the presence of water studied.