In this study, the characteristics of optical fibers for the application in photocatalytic system was investigated using the intentionally designed accessories for spectrometer and radiometer to resolve the problems associated with the conventional system such as cost and structural restrictions from artificial lamp usage, to broaden the application fields into underground, and to utilize solar light in the future. To do this two kinds of optical fibers, plastic optical fiber (POF) and quartz optical fiber (QOF) were compared in terms of characteristics related with light transmittance and absorption and reactivity in TCE degradation.