Leaching of heavy metals from Sedum alfredii Hance biomass was studied with ammonia-ammonium chloride solution as leaching agent. The research was carried out in two phases: 1) a leaching study to determine the zinc extraction efficiency of this leaching agent, and 2) a thermodynamic analysis to identify the likely reactions and stable Zn(Ⅱ) species formed in the leaching systems. Taguchi orthogonal experiment, with four variable parameters, leaching temperature, molar ratio of NH_4Cl to NH_3, leaching time and solid-to-liquid(L/S) ratio, and each at three levels, was used to optimize the experiment parameters by the analysis of variances. The results indicate that leaching temperature has the most dominant effect on metal extraction performance, followed by molar ratio of NH_4Cl to NH_3, solid-to-liquid ratio and leaching time. The optimum condition was obtained as follows: temperature of 60℃, molecular ratio of NH_4Cl to NH_3 of 0.6, leaching time of 2 h and solid-to-liquid ratio of 5-1. The total zinc leaching efficiency under optimum conditions reaches 97.95%. The thermodynamic study indicates that the dominant species produced by the leaching process should be the soluble Zn(NH_3)4_~(2+).