Thionocarbamates are the group of collectors that are mostly used for flotation of sulphide copper minerals, alone or in combination with xanthates depending on a mineralogical composition of the ore. In this paper, the results of the study of application of thionocarbamates in copper slag flotation are presented. Chemical analysis of smelter slag sample obtained from Flotation plant in Bor, Serbia, showed that it contains 3.56% of copper, of which over 73% is in the sulphide form, as well as 0.58 g/t of gold and 11.30 g/t of silver. XRD analysis identified fayalite and magnetite as main minerals present in the slag and SEM-EDS analysis showed that copper is mainly present in the form of sulphide minerals, thus making it suitable for flotation with thionocarbamates. Two thionocarbamates MX 980 and TC 1000 and one xanthate SIPX, along with their mixtures MX 980 + SIPX and TC 1000 + SIPX, were investigated. The influence of parameters such as collector type and dosage, grinding fineness, pulps’ pH and flotation time, on flotation indicators (recovery, yield and copper grade in concentrate) were determined. Smaller dosages of thionocarbamates (40 g/t) provided concentrates with high copper grades, 22.34% (MX 980) and 18.42% (TC 1000) and lower recovery rates, 83.98% (MX 980) and 87.78% (TC 1000), while the increase of dosages to 200 g/t led to the increase of recovery rates for more than 4% and a significant decrease in copper grades. The increase of grinding fineness from 50% to 70% of grain size < 0.074 mm showed a positive impact on flotation indicators, recovery rate, copper grade and yield, for all investigated collectors and their mixtures, while, with the further increase from 70% to 90%, recovery rates continued to increase while copper grades decreased. The increase of pulps’ pH had a positive influence, especially for MX 980, for which recovery rates increased with the increase of pH from 8 to 10 (12). A flotation kinetics test showed that flotation with TC 1000 was the fastest, i.e., recovery rate after 20 min of flotation was over 91%, while recoveries obtained with other collectors were a few percentage points lower.