Amphiphilic sulfo- or amino-containing molecular brushes are synthesized by the radical copolymerization of methacrylic esters containing oligo(ethylene glycol) and/or oligo(propylene glycol) blocks of varying length and arrangement with 2-acrylamido-2-methylpropanesulfonic acid or N -(3-dimethylaminopropyl)methacrylamide in solutions (water, ethyl acetate, toluene). In copolymerization with 2-acrylamido-2-methylpropanesulfonic acid in water, the compositional homogeneity of the copolymers grows appreciably with increasing concentration of initial solutions. It is shown that the structure of macromonomers has almost no effect on their reactivity ratios in copolymerization with N -(3-dimethylaminopropyl)methacrylamide in organic solvents. The synthesized amino-containing molecular brushes exhibit stimuli-responsive properties in aqueous solutions, and the arrangement of hydrophilic and hydrophobic blocks in the side chains of macromolecules affects dependences of the phase transition temperature on polymer concentration and рН.