ABSTRACTA series of three lead borosilicate glasses were synthesized and analyzed for structural information with both ¹¹B and ²⁰⁷Pb solid-state nuclear magnetic resonance (NMR) spectroscopic methods. Results showed that increasing lead content caused lead to take a more active role in the network as a former and that the populations in these sites can be approximately quantified. ²⁰⁷Pb phase-adjusted-spinning sidebands (PASS), ¹¹B magic-angle spinning (MAS), and ¹¹B multiple-quantum MAS (MQMAS) experiments were used to determine structural parameters for the two nuclei. The ²⁰⁷Pb PASS experiment showed that at higher lead content, more covalent bonding was present. This principle was demonstrated in both an overall shift of the spectral resonances and a quantitative change in site ratios. The ¹¹B MAS experiment showed that the ratio of BO₃ to BO₄ units was dependent on the amount of lead and boron, consistent with previous studies. Preliminary ¹¹B MQMAS experiments failed to detect any BO₃^– units, previously hypothesized to exist in this system.