To overcome the limitation of traditional photoluminescent materials, a cost-effective photoluminescence polymer was synthesized by a simple and one-step technique using benzyl alcohol as the starting material and aqueous sulfuric acid as the catalyst. The synthesized photoluminescent polymer showed photoluminescence properties independent of the excitation wavelength together with high thermal stability and excellent mechanical properties. The synthesized photoluminescent polymer was incorporated into different polymers viz. thermoplastic as well as thermoset polymers by melt and solution processes, respectively, to achieve photoluminescent polymer blends. The thermal, mechanical, and photoluminescent properties of the fabricated blends were improved or remained almost the same with the photoluminescence polymer contents, strongly proving that the photoluminescent polymer was well dispersed in the polymeric matrix. The potential applications of the photoluminescence polymer blends were investigated for 3D printing and a fluorescent ink. The study paves a way for the development of photoluminescent materials for various applications.