In order to recover the lead from the zinc leaching residues, a new technology involving selective reduction of lead sulfate to lead sulfide with carbon followed by flotation was investigated. The reduction thermodynamics of PbSO4 was discussed and the effects of molar ratio of C to PbSO4, reaction temperature and time were examined by thermogravimetry (TG) and XRD. Verification tests were further carried out to prove the conclusions of thermodynamic and TG analyses, and the transformation extent could reach 86.45% under the optimal roasting conditions. The galena prepared was then subjected to micro-flotation tests, and the highest lead recovery could reach up to 75.32%.