Abstract: Malachite is a common copper oxide mineral that is often enriched using the sulfidization–xanthate flotation method. Currently, the direct sulfidization method cannot yield copper concentrate products. Therefore, a new sulfidization flotation process was developed to promote the efficient recovery of malachite. In this study, Cu²⁺ was used as an activator to interact with the sample surface and increase its reaction sites, thereby strengthening the mineral sulfidization process and reactivity. Compared to single copper ion activation, the flotation effect of malachite significantly increased after stepwise Cu²⁺ activation. Zeta potential, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF–SIMS), scanning electron microscopy and energy dispersive spectrometry (SEM–EDS), and atomic force microscopy (AFM) analysis results indicated that the adsorption of S species was significantly enhanced on the mineral surface due to the increase in active Cu sites after Cu²⁺ stepwise activation. Meanwhile, the proportion of active Cu–S species also increased, further improving the reaction between the sample surface and subsequent collectors. Fourier-transform infrared spectroscopy (FT-IR) and contact angle tests implied that the xanthate species were easily and stably adsorbed onto the mineral surface after Cu²⁺ stepwise activation, thereby improving the hydrophobicity of the mineral surface. Therefore, the copper sites on the malachite surface after Cu²⁺ stepwise activation promote the reactivity of the mineral surface and enhance sulfidization flotation of malachite.