In this work, samples consisting of BiVO4 with exposed (040) facets coupled with Bi2S3 (Bi2S3/BiVO4) were prepared through a one-pot hydrothermal method, using ethylenediaminetetraacetic acid as directing agent and L-cysteine as sulfur source and soft template. X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy measurements indicated that the Bi2S3 content had a significant influence on the growth of (040) and (121) facets as well as on the morphology of the Bi2S3/BiVO4 samples. When the Bi2S3 content reached 1 mmol, the Bi2S3/BiVO4 samples exhibited a peony-like morphology. The results of transient photocurrent tests and electrochemical impedance spectroscopy measurements confirmed that a more effective charge separation and a faster interfacial charge transfer occurred in Bi2S3/BiVO4 than BiVO4. The enhanced photocatalytic activity of the Bi2S3/BiVO4 samples could be attributed to the improved absorption capability in the visible light region and the enhanced electron-hole pair separation efficiency due to the formation of the Bi2S3/BiVO4 heterostructure. In addition, the Bi2S3/BiVO4 samples showed relative stability and reusability. The simple method presented in this work could be used to fabricate composite photocatalysts with high activity for different applications, such as photocatalytic degradation of organic pollutants, photocatalytic splitting of water, and photocatalytic reduction of carbon dioxide. Peony-like Bi2S3/BiVO4 was prepared using EDTA as directing agent and L-cysteine as sulfur source and soft template; the enhanced photocatalytic activity of Bi2S3/BiVO4 could be attributed to its improved absorption capability and charge separation.