We synthesize poly(oligoaniline)s consisting of multiple oligoaniline units linked by alkane spacers with their structures and properties controlled over three different oxidation states. tert-Butoxycarbonyl (t-BOC)-protected diamino-oligoanilines are synthesized and polymerized with diisocyanatoalkanes to produce t-BOC-protected prepolymers. We obtain the unprotected poly(oligoaniline)s in leucoemeraldine base, emeraldine base, and emeraldine salt oxidation forms by using different deprotection conditions for each of them. Distinct routes to each oxidation form of poly(oligoaniline)s enable exploitation of the crystalline structure, electrochemical activity, or conductivity, which is expected from the oligoaniline-based materials, as well as their excellent processability into thin films that arises from their polymeric nature. The results suggest that new functional materials based on poly(oligoaniline)s may be derived by developing efficient synthetic procedures to control the oxidation states, promising for creation of new nanostructured materials with electrochemical activities. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012