Bi2WO6 nanosheets were synthesized by a hydrothermal method with H2WO4 for the first time. The band structure of Bi2WO6 was investigated on the basis of density functional theory calculations. Bi2WO6 photocatalysts showed photocatalytic activity for the degradation of methylene blue under visible light irradiation. Kinetic studies using radical scavenger technologies suggested that holes were the dominant photo-oxidants. After hybridization with C3N4, the photocatalytic activity of Bi2WO6 was obviously enhanced. The enhanced photocatalytic activity of the C3N4/Bi2WO6 photocatalysts could be attributed to the effective separation of photogenerated e-/h+ pairs. The photogenerated holes on the valence band of Bi2WO6 can transfer to the highest occupied molecular orbital of C3N4via the well-developed interface, causing a reduction in the probability of e-/h+ recombination; consequently, large numbers of photogenerated holes led to the enhancement of the photocatalytic activity.