The interaction of anode and electrolyte chemistry in copper electrorefining is complex. This is especially true with regard to the behavior of Group 15 elements (As, Sb, and Bi). To better understand this system, laboratory electrorefining experiments were conducted using commercial anodes with As/(Sb + Bi) molar ratios of 0.54 and 3.8 and an electrolyte collected from a commercial refinery. The effect of adding thiourea during plating was also examined. Twenty-one hour copper deposits were produced in the laboratory to simulate starter sheet production. The mechanical properties of the electrodeposited copper as measured by an industrially relevant empirical bend test and a one-point bend test developed by UFMG are reported. The crystal structures of the samples were also examined.