Zinc Alumino Lithium borate (ZnAlLiB) glasses of different compositions doped with Cu2+ and Mn3+ ions have been prepared using a conventional melt quenching technique. Fourier transform infrared (FT‐IR) studies have been carried out for ZnAlLiB glasses. The physical properties have been measured. The FT‐IR studies indicate that insertion of Cu2+ ions produces [BO3] and [BO4] basic structural units by breaking the boroxol (B3O6) ring, while manganese ions are found to gradually depolymerize MnO2─B2O3 glass matrix. This report presents the synthesis and FT‐IR studies of zinc alumino lithium borate glasses doped with CuO and MnO2. The local structure of copper and manganese ions in the glass system can be studied.