Characteristics of ITO/polypyrrole (PPy) nano fibers/poly(3-hexylthiophene)/A1 photovoltaic devices prepared by nano template method were studied. PPy nano fibers on ITO glass were formed through nano pores of polymer membrane template using home made special sample holder by electrochemical polymerization in an electrolyte solution of pyrrole and lithium perchlorate as a dopant in acetonitrile. Ordered structure with enhanced interfacial area formed by nano template method enable to fabricate polymeric photovoltaic device with improved photo-conversion efficiency. This nano fiber structures film possesses increased interfacial area, large charge separation area (photoactive zone) and secured charge transportation route. The effect of altering energy levels of PPy by changing doped state was also studied. Device made with nano fiber structure showed enhanced photovoltaic effect than that of overlayed film device. (C) 2004 Elsevier B.V. All rights reserved.