Two novel amphiphilic polyethylene amine terephthalate have been prepared via the glycolsis of polyethylene terephthalate (PET). The product, bis (2-hydroxyethyl terephthalate) (BHET), was converted to the corresponding dialkyl halide, bis(2-chloroethyl) terephthalate (BCET), using thionyl chloride (TC). This dialkyl compound was used for alkylation of dodecyl amine (DOA) and tetraethylenepentamine (TEPA) or pentaethylenehexamine (PEHA) to form the corresponding polyethylene amine terephthalate, i.e., DOAT and DOAP, respectively. Their chemical structure, surface tension, interfacial tension (IFT), and dynamic light scattering (DLS) were determined using different techniques. The efficiency of the prepared polyethylene amine terephthalate to demulsify water in heavy crude (W/O) emulsions was also determined and found to increase as their concentrations increased. Moreover, DOAT showed faster and higher efficiency, and cleaner separation than DOAP.