We investigated the formation mechanism of {111} twins in BaTiO(3) through systematic studies of the effects of various processing parameters on the {111} twin formation, in particular, excess TiO(2), initial particle sizes of raw materials and sintering atmosphere (either oxidizing or reducing). Our study on the effect of excess TiO(2) revealed that the second-phase Ba(6)Ti(17)O(40) particles provided the nucleation sites of the {111) twins. The study on the initial particle size showed that the {111} twins formed during the growth of BaTiO(3) grains around the Ba(6)Ti(17)O(40) particles. The twins, however, Formed only when the Ba(6)Ti(17)O(40) interface and the BaTiO(3) grain boundaries were faceted in an oxidizing atmosphere. In a reducing atmosphere, the Ba(6)Ti(17)O(40) interface and the grain boundaries were defaceted trough), and no (111) twins formed. Based on these experimental observations, we proposed a second-phase (Ba(6)Ti(17)O(40)) assisted formation mechanism of (111} twins in BaTiO(3). The proposed mechanism explained well, all of the observed effects of the processing parameters. The mechanism may also account for the formation of annealing twins in single-phase systems with faceted grain boundaries. (C) 2001 Published by Elsevier Science Ltd on behalf of Acta Materialia Inc.