Heavy metals solid waste based geopolymers were prepared from the major material of fly ash(FA), and metallurgical sludge(MS) or municipal solid waste incineration fly ash(MSWIFA). Mechanism and modification of geopolymers by chemical agents were explored. The results show that the optimal content(by mass) of metallurgical sludge is 15% for FS(metallurgical sludge fly ash) geopolymer, and the optimal chemical agent is dithiocarbamate（DTCR）. Similarly, for FM(municipal solid waste incineration fly ash fly ash) geopolymer, the optimal content(by mass) of MSWIFA is 5%, and the optimal chemical agent is trimercapto s triazine trisodium salt(TMT). With the addition of chemical agent, it restrains the destruction caused by heavy metals, improves the degree of geopolymerization, making the products more homogeneous and compact, and promotes the solidification effect. The geopolymer containing 15% MS and modified by DTCR(sample FS 15 D), and the geopolymer containing 5% MSWIFA and modified by TMT(sample FM 5 T) show good resistance to acid and alkaline attack, which contain heavy metals solid wastes and are modified by chemical agents.