Poly(4-vinylpyridine) (P4VP) brushes were grafted onto a substrate via Cu(0)-mediated atom transfer radical polymerization and 1-pyrenebutyric acid (PBA) was incorporated into the brushes through hydrogen bonding interactions with P4VP by immersing the resulting substrate in PBA solution. Fluorescence measurements performed on the substrate after immersion showed that PBA units formed excimers even after the substrate was rinsed with dichloromethane, which confirms the formation of hydrogen bonds between pyridyl groups in the P4VP brushes and carboxyl groups of PBAs.