TSL flue dust is a waste residue, rich in Zn, generating from the pyrometallurgical process of Cu recycling and constitutes a potential raw material for ZnO production. In order to valorize this waste by introducing a novel process, its selective impurity removal by integrating different commercially viable hydrometallurgical technologies was investigated on both laboratory and pilot scale. Special attention was given to determine the usability of the wastewater originated from the Cu recycling industry as a leaching agent. An average of 83% of Zn could be extracted from the TSL flue dust by employing the wastewater leaching with maximum selectivity. Purification of the leached solution was carried out by subsequently subjecting into cementation, oxidation-precipitation, 2-step neutralization, re-pulping, and drying steps, respectively. Recoverability of the Cu value of the flue dust by controlling cementation time and identification of Mn as the cause of the product color issue were remarkable approaches obtained from the purification process. Commercially salable ZnO (tire grade, purity >99.0%) could be synthesized as the final product by employing this novel process after the verification of technical and economic feasibility.