A novel hyperbranched electroactive azo polyamide containing oligoaniline was synthesized by oxidative coupling polymerization. The detailed characteristics of the obtained polyamide were systematically studied by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance ( 1 H NMR) spectroscopy, and gel permeation chromatography (GPC). The thermogravimetric analysis (TGA) revealed a good thermal resistance of the polymer. The photoisomerization process and doping process of the polymer were monitored with ultraviolet-visible spectroscopy. Further, the electrochemical behavior of the polymer was explored by cyclic voltammogram (CV), and the mechanism of electrochemical oxidation process was studied in detail. The polymer in the HCl-doped form possessed much higher dielectric constants compared with that of the similar linear polymer reported before, mainly due to the highly branched three-dimensional molecular architecture and the high content of oligoaniline segments.