Copper-zinc alloy coatings were deposited on mild steel substrates using pyrophosphate-based electrolytes at room temperature and under continuous current. The use of polyligand electrolytes was also investigated, as well as the influence of organic additives on the composition, morphology and electrochemical properties of the coatings. The results showed that good quality copper-zinc alloy deposits could be produced in pyrophosphate-based polyligand electrolytes, especially with the addition of allyl alcohol.