Although the production of copper and its usage has been known for thousands of years, the search for the optimal process of its production is still in progress. The removal of the negative impacts of a certain technology could cost more, over a period of time, than the initial investment in the selection of the optimal technology process which would consider these effects. Hence, the selection should be supported by the innovative and modern tools, such as the applying of the multi-criteria analysis. This paper presents the implementation of the PROMETHEE/GAIA methodology for the ranking of the appropriate technological pyrometallurgical smelting process for the copper concentrate based on the eleven parameters which recognize the economic, ecological and technical aspects of the technological process. The implementation of the multi-criteria decision-making presented in this paper can be deemed as a contribution to the decision making tools, that is, to the one who makes a decision on the selection of the appropriate technological facility for smelting of the copper concentrates. The decision-makers faced with the practical need of evaluating and selecting the most appropriate technological process for pyrometallurgical copper extraction will get the greatest benefit from this multi-criteria model. The innovative contribution of this paper is also presented in the obtained model which systematically analyzes the ecological, economic and technical parameters of the copper extraction process.