Selenium nanoparticles (SeNPs) were synthesized and stabilized by biopolymers, namely, sodium lignosulfonate (LS) and starch sodium octenyl succinate (OSA). The obtained selenium nanoparticles were studied for their catalytic activity in the reduction of a dye (C.I. Basic Blue 9, methylene blue) by sodium borohydride. The SeNPs-OSA and SeNPs-LS nanoparticles were also dispersed in a photosensitive matrix and studied as polymer composites. The research confirmed the catalytic abilities of the prepared SeNPs in the reduction of the organic dye. Mechanical tests on the polymers and their composites showed an improvement in the composites’ strength in all tested cases. An increase in hardness and Young’s modulus values of the filled materials compared to the pure matrix was found as well.