The incorporation of up to 40 % lead excess into the perovskite lattice of Pb(Zr,Ti)O-3 (PZT) has been investigated. Three independent chemical composition analysis methods confirmed the correct determination of the lead excess, present as Pb2O3. High resolution TEM excludes any second phases and restricts the occurrence of lead excess to the perovskite lattice, suggesting a lead oxide perovskite of the form Pb2+Pb4+O3 with a 4-valent ion on the B-site. PZT containing such lead excess is thus a solid solution of PbZrO3, PbTiO3 and PbPbO3. The measured volume increase of the lattice due to a larger average B-ion matches very well with the calculated behavior based on standard ion radii and the B-ion radius dependence of the unit cell dimensions of PZT crystals. Structure factors as determined from Synchrotron X-ray diffraction are much better compatible with the B-site lead model than with the standard PZT ion lattice.