Bi(Mg3/8Fe2/8Ti3/8)O3, a member of a small group of pure Bi(3+) A site perovskites, exhibiting a high ferroelectric Curie point (Tc), was rapidly synthesized by a sample method of molten salt synthesis. The purity of Bi(Mg3/8Fe2/8Ti3/8)O3 samples is directly affected by the reaction conditions such as the soaking temperature, and the heating and cooling rates. The as-prepared Bi(Mg3/8Fe2/8Ti3/8)O3 particles are well-formed, cube-shaped single-crystals with sizes ranging from 200-300 nm. The chemical states of Bi and Fe ions are Bi(3+) and Fe(3+) in Bi(Mg3/8Fe2/8Ti3/8)O3. UV-vis diffuse reflectance spectra and preliminary photocatalytic experiments indicate that the pure Bi(3+) A site perovskite of Bi(Mg3/8Fe2/8Ti3/8)O3 has a suitable energy bandgap (1.86 eV) and shows obvious photocatalytic activity for the decolorization of methyl blue under visible-light irradiation. The present work suggests potential future applications of Bi(Mg3/8Fe2/8Ti3/8)O3 in photocatalysis and ferroelectric photovoltaic effects.