Sulfuration flotation is the most widely used technology in malachite beneficiation. However, the inhomogeneity of malachite surfaces usually results in a non-uniform sulfuration surface. The motivation of this work is attempt to adopt different functional combination collectors to enhance the sulfuration flotation of malachite. Accordingly, the flotation behaviors and adsorption mechanisms of benzohydroxamic acid (BHA) and sodium butyl-xanthate (SBX) on the surface of malachite were systematically investigated using flotation tests, zeta-potential measurements, Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, and first-principle calculations. The test results of vulcanization flotation showed that the combined collectors of SBX with BHA possessed a higher recovery than only using SBH by 20%, indicating that there may be a synergistic effect between BHA and SBX. The IR and Raman spectroscopy demonstrated that both BHA and SBX could chemically adsorb onto the malachite surface. The density functional theory (DFT) calculation results further indicated that the combined adsorption energy of BHA and SBX was much lower than that of only BHA or SBX, which confirmed the synergistic effects of BHA and SBX on the malachite surface. This work may shed new light on the design and development of more efficient combined flotation reagents.