We report high-yield and efficient size-controlled syntheses of Chalcopyrite CuInS2nanoparticles by decomposing molecular single source precursors (SSPs) via microwave irradiation in the presence of 1,2-ethanedithiol at reaction temperatures as low as 100°C and times as short as 30 minutes. The nanoparticles sizes were 1.8 nm to 10.8 nm as reaction temperatures were varied from 100°C to 200°C with the bandgaps from 2.71 eV to 1.28 eV with good size control and high yields (64%–95%). The resulting nanoparticles were analyzed by XRD, UV-Vis, ICP-OES, XPS, SEM, EDS, and HRTEM. Titration studies by1H NMR using SSP1with 1,2-ethanedithiol and benzyl mercaptan were conducted to elucidate the formation of Chalcopyrite CuInS2nanoparticles.