Pure crystalline BaTiO3 nanoparticles were synthesized by new synthesis route. BaTiO3 nanoparticles were synthesized at 80 °C through refluxing in air atmosphere. BaTiO3 nanoparticles were formed through Na2TiO3 as a chemical intermediate. The concentration of NaOH plays an important role to BaTiO3 phase formation. The concentration of NaOH plays an important role to control the size of BaTiO3.