We report a new available strategy for fabricating 2-dimensional petal-like CdS/dodecylamine (DDA) hybrids with enhanced photoluminescence (PL) by using a method of oil/water interfacial self-assembly. First, water-soluble CdS nanocrystals (NCs) were controllably prepared at the two-phase interface by injecting the Na2S Solution into CCl4 phase, And then, the as-synthesized CdS NCs (ca. 4 nm) were transferred from the water to the CHCl3 phase under the direction of DDA. Finally, through the electrostatic interactions between the positively charged amino of DDA and the negatively charged the ligand of NCs surface, we have successfully fabricated petal-like CdS/DDA hybrids via the interfacial self-assembly between the as-synthesized CdS NCs and DDA. The properties of as-prepared CdS NCs and their hybrids were thoroughly investigated by ultraviolet-visible (UV-vis), transmission electron microscope (TEM), Fourier transform infrared spectra (FT-IR), photoluminescence (PL), scanning electron microscopy (SEM) measurements. We have found that these petal-like CdS/DDA hybrids after interfacial self-assembly exhibit good PL property and higher quantum yield.