Luminescent solar concentrators (LSCs) that incorporate organic dyes face challenges such as self-absorption loss and aggregation-caused quenching (ACQ) as doping concentration increases, limiting the dye loading capacity. Particularly for dyes with a small Stokes shift, losses due to self-absorption or quenching are prominent even at low concentrations, hindering the attainment of high power conversion efficiency (PCE) in LSCs. Additionally, exposure of the dye-impregnated polymer matrix to oxygen, moisture, UV light, and other factors leads to a decrease in luminescence efficiency and stability due to the photooxidation reaction of the phosphor. This study presents a facile approach for enhancement of the efficiency and environmental stability of coumarin 6 (C6) dye-doped polydimethylsiloxane (PDMS) LSC through ultraviolet ozone (UVO) treatment. Photocleavage of the C6 dimer into a C6 monomer through UVO treatment leads to a significant enhancement in luminescence. Additionally, thin SiOx layers formed on both sides of the LSC not only assist in capturing luminescent light more efficiently but also block the penetration of oxygen and moisture into the LSC, resulting improved device stability. UVO-treated LSC shows approximately 32% improvement in PCE compared to bare LSCs and exhibits significantly better stability during the 30-day long-term performance test.