Display omitted •A new technical process was proposed to recover valuable components from GRR.•Zn, Pb and Ga were selectively separated from Ga-rich residues with complex compositions.•High purity Zn and Pb products were obtained by low-temperature vacuum carbothermal reduction.•Clarified the mechanism of metal separation and finally obtained a condensate containing 1.49 % Ga. In this study, the gallium-rich residue (GRR) obtained from phosphorus flue dust (PFD) after phosphorus removal was taken as the research object, and a novel technology for efficient recovery of valuable metals from GRR was proposed. This technology mainly adopted a two-stage vacuum carbothermal reduction process to selectively recover Zn and Pb and concentrate Ga. The feasibility of separating these three metals from GRR was investigated by thermodynamic analysis, and the effects of temperature, reducing agent dosage and holding time on metals recovery were explored. A promising recovery rate of up to 96.84%, 97.98% and 86.32% was achieved for Zn, Pb and Ga, respectively, under the optimal conditions. The purity of Zn and Pb in the condensate reached 98.57% and 80.56%, respectively, which can be used as raw materials for downstream enterprises and have high economic value. Additionally, the resulting Ga-rich condensate contained 1.49 % Ga, which is much higher than other traditional Ga-containing secondary resources, and can be further purified by hydrometallurgical process or other technologies. The whole process has almost no secondary pollution, with remarkable efficiency, providing a new approach for the comprehensive utilization of PFD.