1D α-MoO3/Fe2(MoO4)3 nanocomposite was synthesized by a hydrothermal strategy. Fe2(MoO4)3 nanoparticles were uniformly coated on the surface of α-MoO3. α-MoO3/Fe2(MoO4)3 showed enhanced sensing properties to toluene vapor. It was mainly due to the improved catalytic properties of Fe2(MoO4)3.