Visible light generated as the result of interaction of ionizing radiation with matter can be used for radiation therapy quality assurance. In this work, we characterized the visible light observed during proton irradiation of poly(methyl methacrylate) (PMMA) and silica glass fiber materials by performing luminescence spectroscopy. The spectra of the luminescence signal from PMMA and silica glass fibers during proton irradiation showed continuous spectra whose shape were different from that expected from Čerenkov radiation, indicating that Čerenkov radiation cannot be the responsible radioluminescence signal. The luminescence signal from each material showed a Bragg peak pattern and their corresponding proton ranges are in agreement with measurements performed by a standard ion chamber. The spectrum of the silica showed two peaks at 460 and 650 nm stem from the point defects of the silica: oxygen deficiency centers (ODC) and non-bridging oxygen hole centers (NBOHC), respectively. The spectrum of the PMMA fiber showed a continuous spectrum with a peak at 410 nm whose origin is connected with the fluorescence of the PMMA material. Our results are of interest for various applications based on imaging radioluminescent signal in proton therapy and will inform on the design of high-resolution fiber probes for proton therapy dosimetry.