The adsorption mechanism of three different 0,0'-di-alkyl-dithiophosphate (dtp) collectors, K[S22P(OR)2] with R = Et, i-Bu and i'-Amyl, on the surface of synthetic chalcocite (Cu2S)Was studied by means of solid-state 31P CP/MAS NMR spectroscopy. The morphology changes on the conditioned (Cu2S) surfaces, in the collector concentration range 0.1 - 10 mM, were also monitored with scanning electron microscope (SEM). In order to assign Cu(I)-dtp species on the surface of CU 2S, the corresponding bulk Cu(I)-dtp compounds, which are clusters of the monovalent copper containing either Cu6(antiprismatic) or Cu8(cubic) cores, were synthesised, and characterised by means of solid-state 31P CP/MAS and static 65Cu NMR. Further investigations on the crystal habits of the bulk systems were carried out by powder x-ray diffraction and SEM. A comparative analysis of the 31P chemical shift and chemical shift anisotropy (CSA) data estimated from the experimental NMR spectra of the polycrystalline bulk Cu(l) dialkyldithiophosphate complexes was used for assigning the 31P resonance lines in the NMR spectra of the collector treated CU2S powder samples. The species formed on the synthetic Cu2S surfaces were assigned to polycrystalline phases of: Cu6L6 with L = Et2dtp̄μ, Cu6L6, and Cu 8L6(S) with L = i'-Bu2dtp̄, and 3. Cu 8L6S) with L = i-Amyl2dtp̄. A heterophase autocatalytic step process of both formation and growth of solid Cu xLy (L = R2dtp, x = 6 or 8 and y = 6) complexes on the collector treated CU2S surface is proposed. A possible role of the oxidised form of dithiophosphate collectors, bis[di-alkyl-thiophosphoryl] -disulfane (disulfide), is discussed in terms of a specific self-redox reaction. The second order quadrupolar lineshapes in 65Cu NMR spectra were simulated and the interaction parameters, CQ and nQ, for the bulk dialkyldithiophosphato-copper(I) complexes were obtained