Ternary wittichenite Cu3BiS3 nanocrystals were prepared mechanochemically using a planetary ball mill from elemental copper, bismuth and sulfur in a stoichiometric ratio in only 5 min. The orthorhombic wittichenite Cu3BiS3 was nanocrystalline with an approximate crystallite size of 38 nm ± 9 nm, as confirmed by Rietveld refinement. The nanocrystalline character of orthorhombic Cu3BiS3 was also proven by transmission electron microscopy. The measured Raman spectrum confirmed the formation of pure wittichenite Cu3BiS3. The morphology characterization demonstrated the homogeneity of the sample. The value of the specific surface area for pure mechanochemically prepared Cu3BiS3 after 5 min was 2.7 m2g−1. The optical properties were investigated using UV–Vis absorption and micro-photoluminescence spectroscopy. From the absorption UV–Vis spectrum, the value of the bandgap energy was determined to be 1.52 eV, which creates an assumption for the use of wittichenite Cu3BiS3 in photovoltaic applications. The optoelectrical properties of the prepared Cu3BiS3 nanocrystals were verified by current–voltage measurements in the dark and under white light illumination. The photocurrent increased by 26% compared to the current in the dark at a voltage of 1 V. The achieved results confirmed a very fast and efficient way of synthesizing a ternary wittichenite Cu3BiS3, which can be used for applications in solar cells.