Functionalized poly(butylene succinate) (PBSS), prepared via sulfonation of poly(butylene fiimarate) (PBF), was successfully applied as a novel polymeric dopant for polyaniline (PANI). To obtain a conductive and degradable PANI:PBSS complex, the aniline monomers were polymerized in the presence of a negatively charged poly electrolyte template (PBSS). The prepared polymers were characterized through proton nuclear magnetic resonance (1HNMR), Fourier transform infrared (FT-IR), ultraviolet-visible spectroscopy (UV-visible spectroscopy), scanning electron microscopy (SEM), differential scanning calorimeter (DSC), X-ray diffraction (XRD) and electrical conductivity measurements. The hydrolytic degradation of PANI:PBSS was also investigated based on FT-IR analysis and weight loss. Based on the results, the semi-crystalline structure of PBF was changed to an amorphous structure in PBSS and PANI:PBSS. The PANI morphology in the presence of the small dopant (HCl) was granular, while it changed into a fibrillar shape in the presence of the macromolecular dopant. The electrical conductivity of PANI:PBSS (28.6 S/m) was slightly smaller than that of the HCl-doped PANI (48.4 S/m). The alkaline solution could hydrolytically degrade PANI:PBSS and after 10 days, a weight loss of 45% was observed.