In the present work, we report the preparation by the electrospinning technique and the characterization of poly(3hexylthiophene)-polyethylene oxide-single wall carbon nanotubes (P3HT-PEO-SWCNT) fibers. The SWCNT concentration into the P3HT-PEO matrix is varied from 0.2 to 1%. Optical, electrical, thermal, and morphological properties of the P3HT-PEO-SWCNT fibers are determined. The incorporation of the SWCNT into the P3HT-PEO polymer matrix is determined by SEM, EDS analysis, TEM, FTIR, and Raman. The optical properties are analyzed by the determination of photoluminescence and photoresponse. The stability and degradation temperature of the fibers are determined by TGA. The morphology of the P3HT-PEO-SWCNT fibers depends on the SWCNT concentration, in all cases non-beaded fibers are obtained. It is found that the SWCNT incorporating into the P3HT-PEO fibers increases the conjugation length of P3HT chains. Charge transfer from P3HT to SWCNT is corroborated by photoluminescence and Raman. The P3HT-PEO-SWCNT fibers obtained in this work exhibit interesting optoelectronic properties that could be useful for device applications.