The interest in the incorporation of Sb into the BaTiO3 lattice is based above all on the fact that small additions of Sb (below 0.2 wt% Sb2O3) yield semiconducting ceramics with a resistivity anomaly at the Curie point. Larger amounts of Sb, however, result in insulating samples. This is caused by a different kind of incorporation. In the range of high concentration only a composition as BaO + (1 − x) · TiO2 + x · 1/2 Sb2O3 (for x between 0 and 0.1) yields ceramics which show no crystalline phases other than the perovskite one. This and the structure factors determined by neutron diffraction provide a definite proof that Sb occupies Ti sites. By means of combined electron‐microprobe and X‐ray analysis it is also shown that in the case of excess TiO2 in the BaTiO3 solid solution, Sb partly substitutes Ba sites. Copyright © 1969 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim