The crystal-chemical analysis of seven structures of synthetic and natural lead silicates with formulas Pb2SiO4, Pb11Si3O17, Pb3Si2O7, {Pb4(О(ОН)2)}[SiO4], PbSiO3 (alamosite), Pb7SiO8Cl2 (asisite), and Pb21[Si7O22]2[Si4O13] was performed using the bond-valence method and Voronoi–Dirichlet polyhedra. It was shown that oxygen atoms of cationic units can be unambiguously differentiated from oxygen atoms involved in oxo-centered tetrahedra only using a one-parameter bond-valence equation. In all these structures, the volumes of OPb4 tetrahedra are in the range of 5.8–6.5 A3, and there is a weak negative linear correlation with the bond-valence sum at the oxygen atom. The minimum solid angle (12%) of the Pb–O contact in the OPb4 tetrahedron was found in this group of compounds.