Nanopowders of Bi₂Ti₂O₇ were synthesized by a metallorganic decomposition (MOD) technique. Pure Bi₂Ti₂O₇ nanocrystals formed after annealing at 550°C for 5 min. X‐ray patterns show that Bi₂₀TiO₃₂ is a metastable phase during Bi₂Ti₂O₇ formation. It was found that there were two peaks in the curves of the dielectric response as a function of temperature for pressed nanocrystalline Bi₂Ti₂O₇ samples. The Curie temperature decreases with decrease of grain size whereas the ferroelectric‐ferroelectric phase transition temperature increases. The hysteresis loops observed also suggest that Bi₂Ti₂O₇ might belong to a ferroelectric material.