Two-dimensional nanostructures of Bi–Bi2O3/C hybrid composites were directly synthesized from metal–oleate precursor through a melting-salt process. The Bi–Bi2O3 nanoparticles with the size about 40–100 nm were wrapped by the thin carbon layers. The photocatalytic activities of the as-prepared nanocomposite were evaluated by the degradation of methylene blue (MB), methyl orange (MO) and Rhodamine B (RhB) dyes under UV irradiation. Furthermore, the degradation rate of MB, MO and RhB was approached to 90.8%, 96.2% and 99.7% within 210 min, respectively. The new synthetic procedure is simple, inexpensive and non-toxic and the highly ordered 2-D structure of these nanocomposites has great potential for many future applications.