In the present study, a novel glass system containing Neodymium(III) oxide with BaO, Al₂O₃, and B₂O₃ were created via a popular melt-quenching technique. Nd₂O₃ were added, in different concentrations, instead of B₂O₃ to study its impact on the crystallization, and electro-magnetic behaviors of the prepared poly-crystalline materials. Thermal characteristics via DTA, XRD and SEM techniques were involved to explore the crystallization and structural properties. The magnetic parameters of the prepared glass–ceramics were studied by VSM measurements. As well the electric properties were also explored. BaB₂O₄ and Al(BO₃) phases were firstly crystallized then Ba₃Nd(BO₃)₃ phase was incompletely precipitated instead of BaB₂O₄ phase owing to Nd₂O₃ additions. As well, the internal structure was modified from coarse crystals to fine grain microstructure. The crystallization study proved that the addition of neodymium improved the crystallization process of the BaO–Al₂O₃–B₂O₃ glass system. The VSM and conductivity analysis for the crystalline materials proved that the Nd₂O₃/B₂O₃ substitutions led to an increase in the electrical and magnetic parameters of the investigated materials. The data obtained from the prepared crystalline specimen showed that these materials are with a distinct and promising ferro-electrical property for use in diverse modern applications.