The efficient utilization of inherently conducting polymers in nanotechnological applications faces challenges in processing them into highly ordered structures that yield novel properties. This paper reports a comparative study on the nanocomposites of poly(1-naphthylamine) (PNA), having a fused aromatic ring, and its conductive nanocomposites with polyvinyl alcohol (PVA) and polyvinyl chloride (PVC). The composites were prepared by two different methods: (a) dispersion of PNA in PVA and (b) in situ polymerization of PNA in PVC. These nanocomposites were characterized by UV-visible spectroscopy, TEM, stress, strain, and conductivity measurements. The variation in the nanostructured morphology of PNA particles in PVA as well as PVC matrix in the two cases resulted from the pronounced interaction of PNA with PVA through hydrogen bond, forming a homogeneous matrix that facilitates the formation of a self-assembled network of PNA nanoparticles. In case of PNA/PVC composite, a discrete, agglomerate-free distribution of PNA particles was obtained. The results revealed that an appropriate choice of synthesis conditions offers a possibility to improve not only the processability but also the pattern of distribution as well as the stability of PNA particles. (C) 2008 Wiley Periodicals, Inc. Adv Polym Techn 27: 40-46, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOT 10.1002/adv.20117