A general strategy for realizing the self-assembly of aqueous CdTe nanocrystals (NCs) at the water/oil interface by means of an amphiphilic core-shell hyperbranched polymer has been proposed. Aqueous CdTe NCs were firstly transferred into the chloroform phase in the presence of palmityl chloride functionalized hyperbranched poly(amidoamine) (HPAMAM-PC), and then self-assembled at the water/chloroform interface by decreasing the pH value of the aqueous phase or introducing α-CDs to the aqueous phase. The resulting CdTe/HPAMAM-PC self-assembly film was characterized by fluorescence microscopy, UV-vis, PL, TEM, EDS, FT-IR, DSC and TGA.