Nanoparticles of barium orthotitanate (Ba2TiO4) was obtained using microemulsions (avoiding Ba-alkoxide). Powder x-ray diffraction studies of the powder after calcining at 800 °C resulted in a mixture of orthorhombic (70%) and monoclinic (30%) phases. The high-temperature orthorhombic form present at 800 °C was due to the small size of particles obtained by the reverse micellar route. Pure orthorhombic Ba2TiO4 was obtained on further sintering at 1000 °C with lattice parameters a = 6.101(2) Å, b =22.94(1) Å, c = 10.533(2) Å (space group, P21nb). The particle size obtained from x-ray line broadening studies and transmission electron microscopic studies was found to be 40–50 nm for the powder obtained after heating at 800 °C. Sintering at 1000 °C showed increase in grain size up to 150 nm. Our studies corroborate well with the presence of a martensitic transition in Ba2TiO4. The dielectric constant was found to be 40 for Ba2TiO4 (at 100 kHz) for samples sintered at 1000 °C. The dielectric loss obtained was low (0.06) at 100 kHz.