Until now, it is a great challenge for the controllable synthesis of copper antimony sulfide (CAS) nanocrystals (NCs), as the reactivity of precursors is quite difficult to be controlled during the synthesis process. In the present work, a novel solution-based method is proposed to synthesize CAS NCs by choosing N,N'-diphenylthiourea as the sulfide precursor, which is favorable for balancing the relative reactivity of Cu and Sb ions. It is found that three phases (CuSbS2, Cu12Sb4S13 and Cu3SbS4) of CAS NCs with size tunability were successfully synthesized for the first time. To the best of our knowledge, the lowest reaction temperature of 110 °C and the highest yield over 90% for CAS NCs were also achieved for the first time, which may be considered to be a green synthesis route compared with other conventional methods. Optical properties indicate that the as-prepared CAS NCs have strong optical absorption in the visible light region of the solar spectrum, and we also observed the band gap tunability of CuSbS2 and Cu3SbS4 materials for the first time.