Ternary copper-antimony sulfide nanocrystals (CAS NCs) have attracted increasing attention in photovoltaics and photoelectric nanodevices due to their tunable band gaps in the near-IR regime. Although much progress in the synthesis of CAS NCs has been achieved, the selective synthesis of CAS NCs with controllable morphologies and compositions is preliminary: in particular, a facile method is still in demand. In this work, we have successfully selectively synthesized high-quality CAS NCs with diverse morphologies, compositions, and band gaps, including rectangular CuSbS2 nanosheets (NSs), trigonal-pyramidal Cu12Sb4S13 NCs, and rhombic Cu3SbS3 NSs, by cothermodecomposition of copper diethyldithiocarbamate trihydrate (Cu(Ddtc)2) and antimony diethyldithiocarbamate trihydrate (Sb(Ddtc)3). The direct and indirect band gaps of the obtained CAS NCs were systematically studied by performing Kubelka-Munk transformations of their solid-state diffuse reflectance spectra.