Investigation on the flotation behaviour of enargite (Cu₃AsS₄) and tennantite ((Cu, Fe)₁₂As₄S₁₃) during selective copper flotation was performed using an integrated mineralogical approach. To this end, samples taken from a production block at the Chelopech mine were subjected to a laboratory scale flotation and products characterized through multi-element chemical analyses and mineral mapping using a SEM-based automated mineralogy. Chemistry, modal mineralogy, copper-sulphosalts’ liberation and associations were quantified. Principal component analysis (PCA) was employed to look for relationships between mineralogical features and flotation recovery. High variability in head copper grade was observed in the studied block, with deportment results attributing it to the varied content of enargite and tennantite. Chalcopyrite content was low in the majority of the samples. The close association and the frequently observed interlocking of pyrite and Cu-sulphosalt grains can explain pyrite (and gold) recovery during copper cleaner flotation. Linear equations based on PCA results allow the prediction of Cu-sulphosalts’ recovery with a root mean square error of ±1.32%.