In this work, octyl hydroxamic acid (OHA) was utilized as a collector for galena flotation, and its adsorption kinetics on galena surface was fully studied. The experimental results showed that the optimal pH for the adsorption was 9.5 and the adsorption equilibrium was reached at 2 h. It is important to emphasize that this process was an exothermic, spontaneous, ordered and monolayer adsorption. In addition, the adsorption of OHA on galena surface could change the surface charges and improve the surface hydrophobicity, as identified by zeta potential and contact angle measurements, respectively. XPS analysis demonstrated that OHA chemisorbed on the galena surface mainly through the binding reactions between the two O atoms of -C(=O)–NHOH group and Pb(OH)+ on galena surface at pH 9.5. Flotation experimental demonstrated that 4 × 10-5 mol/L OHA could collect 98.62% of galena at pH 9.5, which was higher than that by sodium isopropyl xanthate (SIPX) under the same experimental conditions.