A new family of multiblock copolymers (PEA-b-AP) based on poly(ester amide) (PEA) and aniline pentamer (AP) with the unique properties of being both electroactive and biodegradable was synthesized via a two-stage active solution polycondensation. The new synthesis approach proceeded smoothly, and avoided the complicated purification steps for separating the intermediate products. The molecular weight of PEA blocks was regulated by varying the nucleophilic/electrophilic monomers feed ratios. The chemical structures of the copolymers were confirmed by both IR and NMR spectra. UV-Vis spectroscopy indicated that the copolymers possessed of the intrinsic electroactivity of AP blocks, and showed three reversible oxidation states. The copolymers had lower degradation rates than the PEA homopolymers with similar molecular weight, and their degradation rates were greatly affected by the proportion of AP blocks. In vitro cell culture studies of the PEA-b-APs revealed that they facilitated the proliferation of RSC96 Schwann cells and displayed a good biocompatibility. These biodegradable copolymers with electroactive function may have great potential for use as nerve repair and regeneration scaffold materials in tissue engineering. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4722-4731