Novel Pb7O6Br2 (1) lead oxybromide was prepared from Pb oxybromide melt by the "rapid quenching" route. Bonding scheme, thermal expansion, and structural properties were studied. The structural features of this unexpectedly complex phase are described on the basis of lone electron pair stereochemical activity and Pb-Br versus Pb-O bonding scheme. The structure of 1 contains a number of cavities, which can be assigned to the self-containments of the lone electron pairs on Pb(2+) cations. "Empty" □Pb4 chains are observed in between of the folding sides of the adjacent strongly corrugated oxocentered [Pb7O6](2+) layers. Highly isotropic thermal expansion of 1 appeared to be unexpected. The possible explanations of such a behavior in 1 are given. The structure of 1 is an interesting example of tetrahedral framework with mixed chemical bonding and is the densest known among Pb oxyhalides with the density of 18.4 tetrahedra/1000 Å(3). Current study shows that oxocentered layers derivatives from α-PbO can be very flexible and form rather dense three-dimensional structural topologies. The properties and structure are compared to other phases crystallizing in the anhydrous PbO-PbX2 (X = F, Cl, Br, I) systems, illustrate the complexity of lead oxyhalides, and reveal new and general pathways for the targeted synthesis of new phases with the Pb-O units of desired dimensionality. The indirect gap value of ∼ 2.04 eV obtained from generalized gradient approximation calculations demonstrates potentially good photocatalytic properties of 1.