A transparent, flexible silicone rubber ([SiO(CH3)2]n) surface was photochemically modified into a photoluminescent material using a 193 nm ArF excimer laser. The photomodified silicone rubber emitted white light under a 325 nm He–Cd laser or a 375 nm light-emitting diode. The chemical bonding of the photomodified silicone rubber was found to be similar to that of a silica-like silicone, as analyzed by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The photoluminescence of the rubber originated from oxygen deficiency centers and peroxy centers of the silica structure in the photomodified silicone rubber. Fine particles 200 nm in diameter were also formed in the photomodified silicone rubber to enhance the intensity of the photoluminescence.