The radioluminescence spectrum of Ge-silica fibres doped with Nd is found to change by the effect of pre-irradiation and thermal annealing. Originally the spectrum consists of a gaussian band centred near 3.1 eV (400 nm). Following the irradiation and heating an additional asymmetric band appears near 2.4 eV (520 nm). On top of this band there is a line spectrum, which can be ascribed to internal transitions of the Nd3+. On the basis of the spectroscopic data and previous results of thermoluminescence measurements, a model is suggested for the luminescence and the effect of the thermal annealing. The blue and green bands are ascribed to an O2- molecular ion and a hole centre near the Nd3+ ion, respectively.