Annually, hundreds of thousands of tons of slags are involved in the reverberator and flash smelting as well as converting operations of Cu-Fe sulfide concentrates to produce matte in the Sar Cheshmeh copper smelter plant, Iran, disposed in the landfill and cooled in air. Due to their relatively high average copper content (about 1.5 wt%), a mineral processing plant based on the flotation process has recently been established to produce thousands of tons of Cu-sulfide concentrate after slag crushing and fine grinding operation. In order to make the flotation process more efficient, more knowledge is required on the form and origin of the copper losses in the slag. To achieve this, mineralogical studies of the slags using optical microscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) methods have been carried out. Mineralogical analyses showed the main part of copper losses into the semi- to fully-crystallized magnetite-rich reverberator and flash slags characterized by crystal–glass matrix ratio ≤ 1 is moderate to coarse particles of Cu-Fe sulfides, i.e., chalcopyrite (CuFeS2) and bornite (Cu5FeS4), that are mainly chemically entrapped. In contrast, the mechanically entrapped fine- to coarse-grain (from 20 up to 200 µm) spherical-shaped of high-grade matte particles with chalcocite (Cu2S) composition containing droplets or veinlets of metallic copper (Cu0) are the dominant forms of copper losses into the converter slags characterized by crystal–glass matrix ratio > 1. From the value recovery point of view, our result show that the fully crystallized slags containing moderate- to coarse-grain copper-bearing particles will result in efficient recovery of a significant amount of entrained copper due to better milling response compared to semi-crystallized ones due to locking the fine- to moderate-grain copper particles in the silicate glassy matrix. Laboratory-scale grinding experiments showed that normal (≤74 μm) to fine (≤44 μm) grinding of high- Cu grade slags lead to a significant increase in the liberation degree of copper particles. in contrast, the increase in fine particle fractions (<37 μm) due to re-grinding or ultra-fine grinding of the originally low-Cu grade slags does not lead to the liberation of copper particles, but it will reduce the efficiency of the flotation process. This study suggests that the highest rate of copper recovery of the slag by the flotation process will be obtained at particle size 80% passing 44 µm which has also reached the optimal liberation degree of copper-bearing particles.