The carrier trapping and recombination mechanisms occurring in Ce-doped silica fibers, produced by a sol−gel technique, are investigated by combining temperature-dependent steady-state X-ray-excited luminescence, wavelength-and timeresolved scintillation measurements, and wavelength-resolved thermally stimulated luminescence, focusing especially on the temperature range from 10 to 320 K. The scintillation decay features a decay time of the order of tens of nanoseconds, characteristic of the parity-and spin-allowed 5d−4f radiative transition of Ce 3+ ions. In addition, a slow and complex decay contribution in the microsecond timescale is detected. We interpret these features as due to the radiative recombination at Ce centers of carriers freed from a continuous distribution of trapping sites in the forbidden gap as well as to the occurrence of an athermal tunneling recombination process between traps and Ce 3+ ions. This interpretation is reinforced by good agreement between independent evaluations of trap depths and lifetimes obtained by both the numerical analysis of scintillation time decays and thermally stimulated luminescence experiments.