A novel hydroxamic acid, N-hydroxy-9,10-epoxy group-octadecanamide (N-OH-9,10-O-ODA), was synthesised by modifying the structure of oleic acid. The carboxyl group of oleic acid was converted into an N-hydroxy amide group, and an epoxy group was introduced into its structure. N-OH-9,10-O-ODA was used as a novel collector in the flotation separation of spodumene from one of its associated gangue minerals, specifically albite. N-OH-9,10-O-ODA exhibits remarkable selectivity, with a stronger affinity for collecting spodumene particles compared to albite particles. Zeta potential measurements and X-ray photoelectron spectroscopic analysis reveal that the adsorption quantity of N-OH-9,10-O-ODA on spodumene surface is comparable to that on albite surface. First-principles calculations demonstrate the diverse adsorption configurations of N-OH-9,10-O-ODA on surfaces of spodumene and albite, leading to its distinct collecting abilities for spodumene and albite particles.