Fly ash that was enriched with lead (Pb), formed as an intermediate in waste lead-acid battery (WLAB) smelting, was recycled by the hydro-electrometallurgy. Characterization of fly ash thereof indicated that the Pb was in the forms of PbSO4 (anglesite) and Pb2OSO4 (lanarkite). Nitric acid and sodium hydroxide were firstly used to study the leaching of the fly ash sample, which was affected by leachant dosage and solid-to-liquid ratio (S/L). At an S/L of 60gL−1, the leachability of Pb was 43% and 67% in 2M acidic and basic solutions, respectively, based on an average 70wt% of Pb in the original fly ash. Anglesite was completely soluble in NaOH and lanarkite was mildly soluble in HNO3. Pb was recovered from the pregnant leach solution within an electrolytic cell constructed with graphite or RuO2/IrO2-coated titanium (Ti-DSA) anodes and a stainless steel cathode. Properties of anodes deposited with lead dioxides were analyzed by cyclic voltammetry. The optimized parameters of electrowinning were 2M NaOH leachant, a current density of 0.75Adm−2 and an electrolytic process duration of 120min, which yielded a Pb removal of higher than 99% and a specific energy consumption of 0.57Whg−1. This process constitutes an eco-friendly and economic alternative to the presently utilized secondary pyrometallurgy for treating lead-containing fly ash.