Here, we report thiol-free thermal-injection synthesis of chalcopyrite (CuFeS2) nanocrystals (NCs) using iron (II) bromide (FeBr2), copper (II) acetaylacetonate (Cu(acac)2), and elemental sulfur (S). Controlled reaction temperature and growth time yield stable and phase-pure ternary CuFeS2 NCs exhibiting tetragonal crystal structure. With increasing growth time from 1 to 30 min, absorption peak slightly red shifts from 465 to 490 nm. Based on spectroscopic ellipsometry analysis, three electronic transitions at 0.652, 1.54, and 2.29 eV were found for CuFeS2 NC film. Also, CuFeS2 NC thin films are incorporated as hole transport layers in cadmium telluride solar cells reaching an efficiency of ~12%.