The structural effects of yttrium (Y) and cerium (Ce) are investigated when substituted for sodium (Na) in a 0.52SiO2–0.24SrO–(0.24−x)Na2O–xMO (where x = 0.08; MO = Y2O3 and CeO2) glass series. Network connectivity (NC) was calculated assuming both Y and Ce can act as a network modifier (NC = 2.2) or as a network former (NC up to 2.9). Thermal analysis showed an increase in glass transition temperature (Tg) with increasing Y and Ce content, Y causing the greater increase from the control (Con) at 493∘C to 8 mol% Y (HY) at 660∘C. Vickers hardness (HV) was not significantly different between glasses. 29Si Magic Angle Spinning-Nuclear Magnetic Resonance (MAS-NMR) did not show peak shift with addition of Y, however Ce produced peak broadening and a negative shift in ppm. The addition of 4 mol% Ce in the YCe and LCe glasses shifted the peak from Con at −81.3 ppm to −82.8 ppm and −82.7 ppm respectively; while the HCe glass produced a much broader peak and a shift to −84.8 ppm. High resolution X-ray Photoelectron Spectroscopy for the O 1s spectral line showed the ratio of bridging (BO) to non-bridging oxygens (NBO), BO:NBO,was altered,where Con had a ratio of 0.7, HY decreased to 0.4 and HCe to 0.5.