Electron paramagnetic resonance (EPR) and optical studies have been carried out on Cu(II)-, VO(II)- and Cr(III)-doped strontium tetraborate glasses to understand the distortion and substitution of these ions. The EPR results of Cu(II) glass indicate that g∥ > g⊥, typical for the tetragonally elongated octahedral site of the Cu(II) impurity. The evaluated covalency parameter 0.788 suggests a moderate covalency for the bonding. By correlating EPR and optical results, the in-plane π-bonding β12 is evaluated as 0.715. In the vanadium-doped glasses, the distortion must be a tetragonally elongated octahedron, similar to Cu(II). However, the EPR studies show that g⊥ > g∥ indicating the tetragonally compressed octahedral site for the ion. The site symmetry is C4V. Supported by the optical absorption, evaluated parameters propose a moderate covalency. The EPR and optical results for Cr(III) glass indicate the distorted octahedral site symmetry in the host lattice. These results further suggest that the bonding between Cr(III) and the ligands is covalent.