For the first time a detailed structural model has been determined which shows how the lone-pairs of electrons are arranged relative to each other in a glass network containing lone-pair cations. High energy X-ray and neutron diffraction patterns of a very high lead content silicate glass (80PbO·20SiO2) have been used to build three-dimensional models using empirical potential structure refinement. Coordination number and bond angle distributions reveal structural similarity to crystalline Pb11Si3O17 and α- and β-PbO, and therefore strong evidence for a plumbite glass network built from pyramidal [PbO(m)] polyhedra (m ~ 3-4), with stereochemically active lone-pairs, although with greater disorder in the first coordination shell of lead compared to the first coordination shell of silicon. The oxygen atoms are coordinated predominantly to four cations. Explicit introduction of lone-pair entities into some models leads to modification of the local Pb environment, whilst still allowing for reproduction of the measured diffraction patterns, thus demonstrating the non-uniqueness of the solutions. Nonetheless, the models share many features with crystalline Pb11Si3O17, including the O-Pb-O bond angle distribution, which is more highly structured than reported for lower Pb content glasses using reverse Monte Carlo techniques. The lone-pair separation of 2.85 Å in the model glasses compares favourably with that estimated in α-PbO as 2.88 Å, and these lone-pairs organise to create voids in the glass, just as they create channels in Pb11Si3O17 and interlayer spaces in the PbO polymorphs.