Glass fiber-reinforced polymer (GFRP) composites have been increasingly used in the construction of civil structures because of their light weight and high strength, tailored flexibility, and corrosion resistance. Such structural materials also present potential for a multi-functional design where functions other than load-carrying capacity, such as thermal insulation, energy supply, and intelligent inspection can be incorporated into one GFRP structural component. This paper further extends this concept by the development of the self-luminous function. In this application, a translucent resin modified with self-luminous powders, together with the nature of glass fibers, is able to illuminate the resulting GFRP composite in darkness and therefore provide the structural members with new architectural and aesthetic features or other service signatures. Mechanical experiments, luminance measurements, and scanning electron microscopy (SEM) imaging have been conducted to examine the self-luminous GFRP composites, and the results are reported in this paper.