Synthesis and study of brush copolymers carrying long PEO side chains and catechol moieties are reported. Kinetics of reversible‐addition‐fragmentation chain‐transfer copolymerization of 2‐(dimethylamino) ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEOMEMA) is studied by size exclusion chromatography (SEC) and 1H NMR spectroscopy, which allow calculating not only copolymerization rate but also the evolution of copolymer composition during copolymerization. Molecular weight Mn and dispersity Ð of the copolymers are determined by SEC with triple detection. Well defined gradient copolymers p(DMAEMA‐co‐PEOMEMA) of various composition with degree of polymerization close to 100 and Ð less than 1.18 are synthesized. For attachment of catechol moieties and introduction of positive charge, DMAEMA units are quaternized with 2‐chloro‐3,4‐dihydroxyacetophenone. The use of tetrahydrofuran as a solvent for that reaction allows obtaining the degree of quaternization close to 100%. Positively charged catechol brush copolymers and their solutions are characterized by 1H NMR, fourier‐transform infrared spectroscopy), and ultraviolet–visible spectroscopy, potentiometric titration, and water contact angle measurements, and their properties are compared with those of similar neutral catechol brush copolymers.