We report here the controlled synthesis of (111) twinned BaTiO₃ microcrystallites, which are widely known for their (110) ferroelectric twins. This (111) twinned structure was obtained through a composite hydroxide mediated process by using amorphous TiO₂ powders. A twin assisted re-entrant growth model is proposed to account for the microstructural aspects determined. It is considered that the (111) twins originate from the Ti–O octahedra of the amorphous TiO₂ powders. The role of oriented aggregation is also discussed.