© 2016 American Chemical Society.[Pb10O4]Pb2(B2O5)Cl12 (1) and [Pb18O12]Pb(BO2OH)2Cl10 (2) were obtained via high-temperature high-pressure experiments. [O12Pb18]12+ and [O4Pb10]12+ oxocentered structural units of different dimensionality are excised from the ideal [OPb] layer in tetragonal α-PbO. 2 is formed with an excess of lead oxide component, and 1 is formed with an excess of borate and halide reagents. The structure of 2 can be visualized as the incorporation of {Pb(10)Cl4(BO2OH)2} clusters into alternating PbO and chloride layers, with the existence of square vacancies in both. However, the structure of 1 is described as the intrusion of [O4Pb10]12+ tetramers linked by disordered Pb(B2O5) groups into a halogen three-dimensional matrix. The structure of 2 contains 10 symmetrically independent Pb positions. The 6s2 lone electron pair is stereochemically active on Pb(1)-Pb(9) atoms, whereas it is inert on Pb(10). All of the Pb coordinations in the structure of 2, in accordance with ECCv (volume eccentric