A scalable liquid exfoliation of layered Bi2S3 employing a mixed-solvent strategy was used for the fabrication of Bi2S3 nanosheets. We found that 10% deionized water in 90% isopropyl alcohol is the best mixed solvent for the efficient and effective exfoliation of layered Bi2S3. These results are consistent with the absorbance spectra and enthalpy of mixing theory. The obtained Bi2S3 nanosheets had few-quintuple layers and were investigated by transmission electron microscopy, atomic force microscopy, and Raman spectroscopy. These Bi2S3 nanosheets can be used to fabricate large-scale thin films by filtration method; the films demonstrated sensitive photoelectric response with the rise and decay response of photocurrent on the sub-second scale under visible light excitation. The electronic structures of bulk and one-quintuple layer Bi2S3 are calculated by first-principle calculation for better understanding of the photoelectric response. A green mixed-solvent processing of Bi2S3 opens up the potential application of Bi2S3 optoelectric films to photoelectric detection and solar energy conversion devices.