Apatite ores are the most important phosphate materials used for the agricultural and livestock chemical production. With the global demand for phosphorous compounds, apatite and other phosphorus-bearing ores are being depleted. The main method of apatite ore enrichment at the moment is the flotation process, the efficiency of which depends on complex heterogeneous processes occurring at the boundary of three phases (“liquid–gas”, “solid–liquid”, and “solid–gas”). Significant influence on the process have the flotation modes and composition of the reagent mixture, which provide a synergistic effect. The purpose of this work was to investigate the reasons for the synergism of surfactants used in apatite ore flotation with fatty acid-based collectors. The object of the study is a monomineral fraction of apatite, separated from the apatite-nepheline ore of Khibiny deposits. In the course of the work, it was found that the mixture of sodium oleate and phospholane PE65 has a synergistic effect on the mineral surface of apatite during foam flotation. The ratio of reagents was determined at which the maximum synergistic effect was observed