In order to solve the shortcomings when removing lead from crude antimony in the traditional antimony smelting, a new process was provided using NaPOs as lead elimination reagent to yield phosphate slag, and it was removed by floating on the surface o f the liquid antimony. Reaction mechanism was clarified by using the TG-DTA and XRD techniques and single factor experiments o f removal lead from crude antimony were engaged. The results show that PbO and NaPO} begin endothermic reaction at 863K (590° C), and the reaction mainly form N a P b /P O J3 and NaPbP04 below 1123K (850°C) and above 1123K (850°C), respectively. Sb20 3 and N aP 03 start the reaction at 773K (500°C) and generate an antimonic salt compound. The reaction product o f the mixture o f PbO, Sb20 3 and NaPO} show that NaPO} reacted with PbO prior when N aP 03 was insufficient, amorphous antimony glass will be generated only when N aP 03 was adequate. Single factor experiments were taken with N aN 03 as oxidizing agent under argon, effect o f reaction time, reaction temperature and dosage o f NaPO} and N aN 03 on smelting results. The average content o f lead in refined antimony was 0.05340% and 98.85% o f lead were removed under optimal conditions; the content o f lead in antimony have meet the requirements o f commercial antimony.