Abstract: The thermodynamics of acetate coordination leaching lead sulfate was studied by thermodynamic equilibrium calculation and confirmatory experiment. First, the rationality of the formation constant of Pb(OH)₆^4- was evaluated by the thermodynamic calculation of the Pb(OH)₂-H₂O system. This showed that the calculated results were obviously inconsistent with the properties of Pb(OH)₂ amphoteric compound if the existence of Pb(OH)₆^4- was considered, so it was not recommended to use it. Then, the thermodynamic equilibrium diagrams of acetate coordinated leaching of lead sulfate were calculated and drawn. The results showed that under different total acetate concentrations, the pH range of 6-9 was more favorable for acetate leaching of lead sulfate, and Pb(Ac)₄^2- was the main species in this pH region. In addition, the higher the total acetate concentration, the higher the concentration ratio of Pb(Ac)₄^2- to free Ac^- in the leachate, which indicated that the acetate utilization rate of leaching lead sulfate increased with the total acetate concentration. Moreover, according to the principle of electric neutrality, conservation of mass and simultaneous equilibrium, the lgc-Na/Ac_T diagram of each dissolved species was calculated and drawn after the equilibrium was achieved when lead sulfate leached from the initial liquid with different ratios of HAc and NaAc. It was found that the lead concentration in the leaching solution increased with the increase of the proportion of sodium acetate in the initial solution when the total acetate was constant, and the confirmatory experiment results were generally consistent with the thermodynamic calculation ones.