Antimony in smelted copper anodes has been shown to cause problems in electrorefining including brittleness of starter sheets. In order to improve deposit properties, a study was conducted examining the effect of anode chemistry on cathode ductility and electrolyte chemistry. Two industrial anodes with different molar ratios of As/(Sb+Bi) were used in laboratory electrorefining experiments with commercial electrolyte, and the addition of commercial glue and Avitone. The ductility of 21-hr copper deposits was evaluated by a 180° bend test. X-ray diffraction (XRD) and metallography were performed on unbent specimens to characterize the deposit structure. Increasing the anode As/(Sb+Bi) molar ratio from 0.54 to 3.8 resulted in an increase, on average, from four to eight bends to failure in cathode material produced. Significantly lower concentration of antimony (V) in the electrolyte was detected when operating with the higher molar ratio anode. The presence of (111) and (200) planes was noted in cathode material produced from the higher molar ratio anode suggesting that mixed growth character could be responsible for the observed increase in bend test results. The ductility of the starter sheet materials was improved by a higher anode molar ratio.