Here, we report the synthesis of Bi2WO6/carbon nanofibers (CNFs) composite with a unique surface morphology, i.e., its surface was fully decorated with crisscrossed Bi2WO6 nanoplates, via two solvothermal steps using ethanol and ethylene glycol as solvent medium in the first and the second step, respectively. Such composite demonstrated significant enhancement for photocatalytic activity relative to Bi2WO6 and mechanical mixture of Bi2WO6 with CNFs, leading to the highest degradation rate of methyl orange (MO) using the composite catalyst under visible light irradiation where up to 92% of MO could be degraded within 360min period. We attribute this to an efficient separation of photogenerated electrons and holes due to the formation of heterostructure between Bi2WO6 and CNFs in the composite.