Polymer flooding emulsions and microemulsions caused by tertiary oil recovery technologies are harmful to the environment due to their excellent stability. Two cationic hyperbranched polyamidoamines (H-PAMAM), named as H-PAMAM-HA and H-PAMAM-ETA, were obtained by changing the terminal denotation agents to H-PAMAM, which was characterized by ¹H NMR, FT-IR, and amine possession, thereby confirmed the modification. Samples (300 mg/L) were added to the polymer flooding emulsion (1500 mg/L oil concentration) at 30 °C for 30 min and the H-PAMAM-HA and H-PAMAM-ETA were shown to perform at 88% and 91% deoil efficiency. Additionally, the increased settling time and the raised temperature enhanced performance. For example, an oil removal ratio of 97.7% was observed after dealing with the emulsion for 30 min at 60 °C, while 98.5% deoil efficiency was obtained after 90 min at 45 °C for the 300 mg/L H-PAMAM-ETA. To determine the differences when dealing with the emulsion, the interfacial tension, ζ potential, and turbidity measurements were fully estimated. Moreover, diametrically different demulsification mechanisms were found when the samples were utilized to treat the microemulsion. The modified demulsifiers showed excellent demulsification efficiency via their obvious electroneutralization and bridge functions, while the H-PAMAM appeared to enhance the stability of the microemulsion.