A series of lead silicate glasses, spanning the broadest reported range of lead contents (up to 83 mol% PbO), were prepared, on which the following spectroscopic observations were made: 29Si magic angle spinning nuclear magnetic resonance, time of flight mass spectroscopy, raman spectroscopy and fourier transform infrared spectroscopy. For bulk, splat-quenched samples, infrared results indicate that the lever rule is approximately followed until about 60 mol% PbO, though with considerable dissociation of the stoichiometric groups into silicate units with lesser and greater numbers of non-bridging oxygens. For roller-quenched samples, nuclear magnetic resonance data are consistent with a statistical distribution up to this lead concentration. Above 60 mol% PbO, added oxygen remains associated with lead to form a separate lead oxide glass network. The evidence for this comes from each of the spectroscopic techniques employed. A quantitative distribution of PbO is given.