Alkali boroaluminosilicate glasses with composition of 56SiO₂–20B₂O₃–3Al₂O₃–8Na₂O–8K₂O–5BaO containing 0–9 mol% cerium oxide (CeO₂) were synthesized at 1500 °C using a conventional melt-quench method. Structural evolution of the as-prepared glasses was studied using infrared and Raman spectroscopy and the glasses' physical properties were characterized. The structural parameter based on the Yun, Dell and Bray model was revised by factoring multiple oxides, including CeO₂, into the computation of the ratio of alkali oxide to boron trioxide, and was used to describe the glasses' structural states divided into three categories with 3–4% as the critical content that marks the onset of drastic variations in glass structure and properties. The addition of CeO₂ below 3% are absorbed by reedmergnerite- and danburite-like groups producing one non-bridging oxygen (NBO) on the silica tetrahedrals and disconnecting tetrahedral borate [BO₄] from tetrahedral silicate [SiO₄]. Addition of CeO₂ above 3% allows the additional oxygen to combine with reedmergnerite- and danburite-like units producing two NBOs on [SiO₄] and also one or two NBOs on trigonal planar borate [BO₃] at the expense of [BO₄]. Further addition of CeO₂ beyond 5% will cause the extra NBOs to gradually combine with the disconnected boron triangles to form boron tetrahedrals in addition to continuous depolymerization of the Si–O network. Network depolymerization, enhanced linkage by charge compensation and improved compactness because of close packing are proposed as the cause of diverse variation trends in physical properties in the presence of CeO₂ below and above 3–4%, respectively. The revised structural parameter analysis is explainable by the correlation between the observed structural evolution and the physical properties, and thus, can be a useful reference for constituents' regulation of CeO₂-doped borosilicate radiation resistant glasses.