Wittichenite (Cu₃BiS₃) nanocrystals have been synthesized utilizing a hot-injection method. They have been characterized in detail. Cu₃BiS₃ nanocrystals possessed a band gap of 1.56 eV, and the corresponding nanocrystal-film shows a clear photoresponse in I–V measurements. Our work illustrates that Cu₃BiS₃ nanocrystals have potential in the application of solar cells.