Copper antimony sulfide (CAS) has been proposed as low toxicity and earth abundant absorber materials for thin film photovoltaics due to their suitable optical band gap, high absorption coefficient and p-type electrical conductivity. The present work reports the formation of copper antimony sulfide by chemical bath deposition using sodium citrate as a complexing agent. We show that by tuning the annealing condition, one can obtain either chalcostibite or tetrahedrite phase. However, the main challenge was co-deposition of copper and antimony as ternary sulfides from a single chemical bath due to the distinct chemical behavior of these metals. The as-deposited films were subjected to several trials of thermal treatment using different temperatures and time to find the optimized annealing condition. The films were characterized by different techniques including Raman spectroscopy, X-ray diffraction (XRD), profilometer, scanning electron microscopy (SEM), UV-vis spectrophotometer, and Hall Effect measurements. The results show that the formation of chalcostibite and tetrahedrite phases is highly sensitive to annealing conditions. The electrical properties obtained for the chalcostibite films varied as the annealing temperature increases from 280 to 350 degrees C: hole concentration (n) = 10(17)-10(18) cm(-3), resistivity (rho) = 1.74-2.14 Omega cm and carrier mobility (mu) = 4.7-9.26 cm(2)/Vseg. While for the tetrahedrite films, the electrical properties were n = 5 x 10(19) cm(-3), mu = 18.24 cm(2)/Vseg, and rho = 5.8 x 10(-3) Omega cm. A possible mechanism for the formation of ternary copper antimony sulfide has also been proposed. (C) 2017 Elsevier B.V. All rights reserved.