Efficient utilization of inherently conducting polymers in nano technological applications faces the challenge to assemble them into highly ordered structures which may yield novel properties. The present study reports for the first time the synthesis and characterization of nanostructured poly (1-naphthylamine) (PNA) dispersed polyvinyl alcohol (PVA) composites. The composites were prepared by loading PNA from 2 wt% to 10 wt% in PVA in aqueous as well as nonaqueous media. The composites were characterized by UV-visible spectroscopy, TEM, stress-strain studies, electrical conductivity measurements and moisture absorption studies under controlled humidity. A discrete but uniform distribution of nanoparticles was obtained in PNA/PVA composites synthesized in water having particle size between 5 and 30 nm. A self assembled network of nanostructured PNA particles was obtained in case of PNA/PVA composites synthesized in N-methylpyrolidone (NMP) with particle sizes between 10 and 65 nm. The variation in the nanostructured morphology of PNA particles in PVA matrix in the two cases resulted from the pronounced interaction of PVA with NMP through hydrogen bonding. This leads to the formation of a homogeneous matrix that facilitates the formation of a self assembled network of PNA nano particles. In case of PNA/PVA composites synthesized in water, lower affinity of PVA towards water was responsible for a discrete, agglomerate free distribution of PNA particles. We have found that the PNA/PVA nano composite synthesized in water exhibited good mechanical properties and electrical conductivity (8.1 x 10 (1) S/cm) as well as lowest moisture absorption (4 wt%) which holds potential for use in semiconductor and biomedical devices. (C) 2008 Elsevier B.V. All rights reserved.