In this paper, we present a facile method of synthesis and modification of poly(glycidyl methacrylate) brushes with 6-aminofluorescein (6AF) molecules. Polymer brushes were obtained using surface-grafted atom transfer radical polymerization (SI-ATRP) and functionalized in the presence of triethylamine (TEA) acting both as a reaction catalyst and an agent preventing aggregation of chromophores. Atomic force microscopy (AFM), FTIR, X-ray photoelectron spectroscopy (XPS) were used to study the structure and formation of obtained photoactive platforms. UV-Vis absorption and emission spectroscopy and confocal microscopy were conducted to investigate photoactivity of chromophores within the macromolecular matrix. Owing to the simplicity of fabrication and good ordering of the chromophore in a thin nanometric layer, the proposed method may open new opportunities for obtaining light sensors, photovoltaic devices, or other light-harvesting systems.