This study examines and compares the internal structure conjugated polymeric fibers fabricated by electrospinning with cast films. Despite rigidity of polymer chain and the inability of its molecular chains to entangle to form viscoelastic jets, regioregular poly(hexyl-3-thiophene) (P3HT) exhibited the remarkable capability to be electrospun when the solution was subjected to gelation. In order to investigate the influence of additional mechanical stretching on the fibers, P3HT was electrospun with the aid of a rotating disc collector. Structure of electrospun fibers was probed via characterization techniques such as differential scanning calorimetry (DSC), Fourier transform infrared and photoluminescence (PL) spectroscopies. The findings indicated internal structural modifications developed within P3HT fibers, as a consequence of additional mechanical stretching induced by the rotating collector. Polarized FTIR and PL spectroscopies suggested that the molecular chains were aligned along the fiber axis. Electrical conductivity of iodine doped P3HT electrospun fibers was between 3 x 10(3) S/m and 6 x 10(3) S/m. (C) 2010 Elsevier B.V. All rights reserved.