Antimony is one of the world’s scarcest metals and is listed as a Critical Raw Material (CRM) for the European Union. To meet the increasing demand for metals in a sustainable way, one of the strategies that could be implemented would be the recovery of metals as by-products. This would decrease the amount of hazardous materials filling mining dumps. The present study investigates the potential for producing antimony as a by-product at the Olympias separation plant in Northern Greece. This plant works a skarn mineralization that shows interesting amounts of Sb. Boulangerite (Pb5Sb4S11) reports on Pb concentrate levels reached 8% in the analyzed product. This pre-enrichment is favorable in terms of boulangerite recovery since it can be separated from galena through froth flotation. Boulangerite distribution in the primary ore is quite heterogeneous in terms of the inclusion relationships and grain size. However, a qualitative assessment shows that the current Pb concentrate grain size is too coarse to successfully liberate a good amount of boulangerite. The use of image analysis and textural assessments is pivotal in determining shape factors and crystal size, which is essential for the targeting of flotation parameters during separation. The extraction of antimony as a by-product is possible through a two-step process; namely, (i) the preliminary concentration of boulangerite, followed by (ii) the hydrometallurgical extraction of the antimony from the boulangerite concentrate. The Olympias enrichment plant could therefore set a positive example by promoting the benefits of targeted Sb extraction as a by-product within similar sulfide deposits within the European territory.