In this study, a new lead (Pb) and chlorine (Cl) recovery process via the thermal co-treatment of Municipal solid waste (MSW) incineration fly ash (FA) and waste cathode-ray tubes (CRT) was developed and the synergistic effects under different CRT ratios, temperatures, and residence times were comprehensively investigated. Thermogravimetric experiments revealed that the co-processing of FA and CRT exhibited a remarkable synergistic effect as evidenced by the considerable increase in mass loss and mass-loss rate when compared with the theoretical values. When the mixtures with 50% CRT addition was treated at 1200 °C for 60 min, Pb removal rate reached the maximum value of 98.67%, and the Cl removal rate considerably increased by 37.32% compared to that with FA treatment alone. Additionally, the Cl content in the residue was < 2%. It was mainly attributed to the volatilization of chlorides, such as PbCl2, NaCl, and KCl. CaCl2 generated from the decomposition of CaClOH in FA was conducive to improve Pb removal in CRT through indirect chlorination and destroying the glass structure in CRT. Co-processing of FA and CRT demonstrates promising potential for several benefits, including the reduction in melting temperature, recovery of Pb and Cl from secondary fly ash, and the reutilization of calcium-rich slag.