Surfactant-free CuInS2 (CIS) nanocrystals (NCs) were synthesized by replacing organic capping ligands with inorganic ions S(2-). The efficacy of ligand exchange was probed by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-vis spectroscopy, and Fourier-transform infrared (FTIR). The surfactant-free CIS NCs films were obtained by drop-casting onto the clean FTO glass. The electrical conductivity and electrocatalytic activity of CIS NCs films were sharply increased due to the improved interparticle coupling after ligand exchange. When the surfactant-free CIS films were used as counter electrode (CE) in dye-sensitized solar cells (DSSCs), a conversion efficiency of η = 5.77% was achieved without sintering.