Electron spin resonance (ESR) spectroscopy does not appear to have found a wide use when compared with other structural analysis methods, especially spectroscopy techniques, utilized in the glass industry. The method, however, provides a good means for supporting the structural information obtained from other spectroscopic methods. Because of its ability to detect and differentiate the paramagnetic ions at low concentrations, ESR spectroscopy is commonly used as a quantitative and qualitative analysis method for evaluating transition metals. This study showed the behavior and interaction of paramagnetic 3d transition metal ions using ESR spectroscopy for the soda-lime-silicate based glasses. For this reason, it revealed the existence of paramagnetic (Fe3+, Cr3+, Mn2+ and Cu2+) transition metal ions in soda-lime-silicate glass and their spectral trends studied at addition levels up to 2.0% mol. Additionally, ESR spectra of Fe3+-Cr3+, Fe3+-Mn2+ and Fe3+-Cu2+ added soda-lime-silicate glass samples were studied to show the effects of the different transition metals on Fe3+ containing glasses. The final point of study is that the approach to quantify the ESR spectra with the concentration of paramagnetic metal ions in glass. In this way, this study gives structural information about the used glass and so lightens the locations of used metal ions.