Pure mineral flotation experiments, zeta potential testing, and infrared spectroscopy were employed to investigate the interfacial reactions of oleic acid (collector), sodium dodecyl benzene sulfonate (SDBS, synergist), and rhodochrosite in an anionic system. The pure mineral test shows that oleic acid has a strong ability to collect products on rhodochrosite. Under neutral to moderately alkaline conditions, low temperature (e.g., 10℃) adversely affects the flotation performance of oleic acid; the addition of SDBS significantly improves the dispersion and solubility of oleic acid, enhancing its collecting ability and flotation recovery. The zeta potential test shows that rhodochrosite interacts with oleic acid and SDBS, resulting in a more negative zeta potential and the co-adsorption of the collector and synergist at the mineral surface. Infrared spectroscopy demonstrated that when oleic acid and SDBS are used as a mixed collector, oleates along with -COO^- and -COOH functional groups are formed on the mineral surface, indicating chemical adsorption on rhodochrosite. The results demonstrate that oleic acid and SDBS co-adsorb chemically on the surface of rhodochrosite, thereby improving the flotation performance of the collector.