As a photocatalyst, barium titanate (BaTiO3) has shown a great potential in photocatalytic water splitting for hydrogen evolution. In this work, BaTiO3 nanoparticles were synthesized at room temperature conditions under ambient pressure. The small particle size below 10 nm plays a key role in suppressing the recombination of photo-induced carriers, and thus promoting the photocatalytic activity. The photocatalytic hydrogen evolution rates of BaTiO3 (BTO-R) synthesized at room temperature are 8 and 2.9 times that of commercial BaTiO3 (BTO-C) in the presence and absence of triethanolamine (TEOA) as a sacrificial agent, respectively. This work provides a good example on size control, low-cost synthesis and photocatalysts' design.