We synthesized chemically well-defined brush (i.e., comb-like) polymers bearing guanine, cytosine, uracil, or thymine moieties at the bristle ends. The polymers were stable up to 220 degrees C and were readily solution-processable, yielding high-quality films. Interestingly, the brush polymers favorably self-assembled to form molecular multibilayer structures stabilized by hydrogen bonding interactions among the nucleobase moieties at the bristle ends, which provided nucleobase-rich surfaces. The multibilayer-structured polymer films showed high water affinity. They also displayed selective protein adsorption, suppressed bacterial adherence, facilitated cell adhesion, and exhibited good biocompatibility in mice. The brush polymer DNA-mimicking comb-like polymers are suitable as biomaterials and in protein separation applications. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1151-1160