Radiation effects in oxide glass as external β-irradiation has been investigated by Raman spectroscopy, Cr3+ luminescence and EPR spectroscopy to analyze microstructure evolution. Comparison between simplified and complex glasses (high-level nuclear waste glass analogue) was undertaken. Migration and segregation of sodium have been confirmed on simplified irradiated glasses by a polymerization increase and dissolved oxygen presence. Densification under irradiation has also been demonstrated with the increase of three-membered silicate rings in silicate glass and the decrease of the average Si–O–Si angle in the borosilicate glass. In both glasses, Cr3+ crystal field was increased, suggesting a Cr–O length decrease. The complex borosilicate glass responds differently: densification effect and Na segregation were not detected. Under β-irradiation, electron-trapping processes on Cr6+ occurred, forming Cr4+ and Cr5+ species.