Abstract: Willemite is a common component of zinc and lead metallurgical slags that, in the absence of effective utilization methods, cause serious environmental problems. To solve this problem and increase zinc recovery, we proposed a novel extraction method of zinc from willemite by calcified roasting followed by leaching in NH₄Cl-NH₃·H₂O solution. The thermodynamics and phase conversion of Zn₂SiO₄ to zinc oxide (ZnO) during calcified roasting with CaO were investigated. The mechanism of mineralogical phase conversion and the effects of the CaO-to-Zn₂SiO₄ mole ratio (n(CaO)/n(Zn₂SiO₄)), roasting temperature, and the roasting time on zinc-bearing phase conversion were experimentally investigated. The results show that Zn₂SiO₄ was first converted to Ca₂ZnSi₂O₇ and then to ZnO. The critical step in extracting zinc from willemite is the conversion of Zn₂SiO₄ to ZnO. The zinc percent leached in the ammonia leaching system rapidly increased because of the gradual complete phase conversion from willemite to ZnO via the calcified roasting process.