This study presents the synthesis and properties of new polymeric materials in form of composites with photoluminescent filler. As a main monomer a bisphenol A glycerolate (1 glycerol/phenol) diacrylate (BPA.DA) was used. In order to obtain the appropriate viscosity of the polymerization system, three active diluents (methyl methacrylate, N-vinyl-2-pyrrolidone and 2-hydroxyethyl methacrylate) were applied. In role of photoluminescent dopant the copolymer of N-vinyl-2-pyrrolidone with 2,7-(2-hydroxy-3-methacrylo-yloxypropoxy)naphthalene, in form of powder was adopted. The compositions were prepared with an increasing amount of filler: 0, 0.5, 1, 2, 5, 10% w/w. After polymerization reaction, samples which generating of green-yellow light by excited by UV radiation were obtained. The influence of the increasing luminescent filler content on the selected properties of the composites was evaluated. The thermal and mechanical behaviors of composites were determined by means of differential scanning calorimetry (DSC), and Shore D hardness. Moreover the chemical structure of polymeric materials were confirmed by the attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR) method. These results shown that the incorporation of the photoluminescent filler into structure of compositions can be interesting method of synthesis e.g. stable and functional polymeric coatings or optical fiber sensors.