NaBiO3/Bi(C2O4)OH composite spindle nanorods were synthesized on a large scale at room temperature by simply using sodium bismuthate and oxalic acid as the reactants. The microstructure and properties of the sample were characterized in detail. The photocatalytic activity of the sample was investigated by photocatalytic oxidation of Rhodamine B under visible-light illumination. The results showed that the sample has excellent photocatalytic activity compared with sodium bismuthate and Bi-based hydroxy oxalate.