Flue dust waste coming from a copper (Cu) smelting company has been valorized using a newly developed metallurgical process with the aim of recovering a dust concentrated in valuable metals, such as lead (Pb) and zinc (Zn), and studying the feasibility of replacing anthracite with biochar as reducing agent. Metallurgical trials using different mixtures of reducing agents have been performed in a furnace at 1400 °C. This furnace employs a high-power thermal plasma (HPTP) system as energy source. Using copper as the base metal, pellets containing a mixture of the waste, different reducing agents, and binder were introduced into the furnace for their dissolution. Recovery yields in the range of 45–85 wt.% for Pb and Zn were obtained in the flue dusts. All the trials proved the effectiveness of the developed process to enrich the flue dusts in valuable metals, including those only using biochar as reducing agent. Further trials will be carried out in order to better control the parameters involved in the metallurgical process developed and improve its efficiency.