Multicentered initiators for the controlled (pseudoliving) radical polymerization are synthesized via polymer analog transformation of hydroxyl-containing polyimides based on o-aminophenols. Conditions providing variations in the degree of functionalization of polyimides by initiating 2-bromoisobutyrate groups are determined, and optimum conditions for the preparation of macroinitators containing the above groups in each repeat polyimide unit are found. Via the method of controlled radical polymerization with the atom transfer on multicentered macroinitiators in the presence of complexes of univalent copper halides, graft copolymers of poly(methylmethacrylate) on polyimide backbone are obtained. Molecular-mass characteristics of graft copolymers are studied via multiple-detection size-exclusion liquid chromatography. Preparation of graft copolymers (polymer brushes) with a homogeneous grafting density and a homogeneous length of side chains necessitates grafting of the side chain on the polyimide initiator, which contains initiating groups in each repeat unit.