Thiophosphate compounds have attracted much attention in coordination chemistry, but their deep adsorption mechanism remains underexplored as flotation collectors. The flotation performance and adsorption mechanism of a novel (dibutoxy-thiophosphorylsulfanyl)-acetic acid (CDDP) chelating collector on azurite surfaces were studied by micro-flotation tests, zeta potential measurements, and Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM) analysis. The micro-flotation results indicated that CDDP exhibited superior collecting performances to direct flotation recovery of azurite and floated over 91.44% of azurite at pH 7. For sodium isopentyl xanthate (NaIX) and Benzohydroxamic acid (BHA) collectors, the addition of Na₂S still did not show good collection performance. The results of zeta potential, FTIR, XPS and FE-SEM measurements, all confirmed that CDDP showed a better affinity to azurite surfaces than NaIX and BHA. Furthermore, XPS and FE-SEM provided obvious evidence that CDDP could easily react with Cu²⁺ sites on azurite surfaces. Using the density functional theory (DFT) method, the collection capacity of azurite was CDDP > BHA > NaIX, which exactly matched the micro-flotation results. In addition, this study provided an atomic-scale understanding of the structure–property relationship of CDDP as chelating agents for copper mineral flotation.